Compounds and compositions containing silicon and/or other heteroatoms and/or metals and methods of making and using them

ABSTRACT

The present invention relates to compounds, intermediates, compositions, and methods of making compounds and intermediates related to the compounds of Formula (I) and/or Formula (II) and/or Formula (III) and/or Formula (IV) and/or Formula (VI) and/or Formula (VII) as disclosed herein wherein the various substituents are as defined in the written description.

This application claims priority under 35 USC §119(e) to U.S.Provisional Application 60/855,428 filed Oct. 31, 2006, the entirecontents of which is incorporated by reference in its entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

This invention was made through the support of National ScienceFoundation Grant No. CHE-0450722. The Federal Government may retaincertain license rights in this invention.

FIELD OF THE INVENTION

The present invention relates to compounds, intermediates, compositions,and methods of making compounds and intermediates related to thecompounds of Formula I and/or Formula II and/or Formula III and/orFormula IV and/or Formula VI and/or Formula VII:

wherein A is a member selected from the group consisting of silicon,platinum, rhodium, boron, arsenic and palladium;

X and X′ are independently an aliphatic hydrocarbon chain or aromaticgroup which may be selected from one or more of the following alkyl,alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, wherein all of thealkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl groups maycontain one or more heteroatoms selected from the group consisting ofnitrogen, phosphorous, arsenic, antimony, bismuth, germanium, tin,oxygen, sulfur, selenium, tellurium, boron, aluminum, gallium, indium,germanium, and silicon, and wherein all of the alkyl, alkenyl, alkynyl,aryl, heteroaryl, heterocyclyl groups also may be optionally substitutedby one or more of the following, alkyl, alkenyl, alkynyl, aryl,heteroaryl, heterocyclyl, halo, cyano, oxo, hydroxy, mercapto, sulfonyl,sulfoxy, amino, imino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, nitroso, and thioxo. All of these substituentsmay, in turn, be optionally substituted with one or more substituentsindependently selected from the group consisting of halogen, hydroxy,cyano, carboxy, thiol, sulfo, nitro, nitroso, oxo, thioxo, and imino.

R₁, R₂, R₃, and R₄ are each independently selected from the groupconsisting of alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl,halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy, amino, imino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,nitroso, and thioxo or

R₁ and R₂ together with the atoms connected to them or R₃ and R₄together with the atoms connected to them may form a spiro C₄₋₈cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; or

R₁ and R₃ together with the atoms connected to them or R₂ and R₄together with the atoms connected to them may form a C₃₋₁₀ cycloalkylgroup that may optionally contain one or more heteroatoms selected fromthe group consisting of nitrogen, phosphorous, arsenic, antimony,bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium, boron,aluminum, gallium, indium, germanium, and silicon.

Y is a counterion such as an alkali metal or other appropriatepositively charged ion.

BACKGROUND OF THE INVENTION

U.S. Pat. No. 4,837,339 to Sato (Sato '339) discloses the synthesis of4-substituted-1,2,3,6-tetrahydrophthalic acid anhydride compoundsrepresented by the below formula A:

where R₁ represents a lower alkoxy group, and R₂ and R₃ each representsa lower alkyl group or a lower alkoxy group, said4-substituted-1,2,3,6-tetrahydrophthalic acid anhydride being liquid.The above compounds from formula A can be made by a Diels Alder typereaction wherein a 2-substituted-1,3-butadiene is reacted with maleicacid anhydride to generate the compounds as shown in Formula A. Thegeneral reaction scheme is shown below:

The compounds generated by the above reaction are useful as startingmaterials for silicone-containing polyester resins, polyamide resins andaddition type polyimide resins; silane coupling agents, particularly,coupling agents for polyimide resins; plasticizers for vinyl chlorideresins or the like, curing agents for epoxy resins and the like.

However, the present above reaction scheme suffers from severaldrawbacks including relatively poor yields, and relatively poor controlof regiochemistry. Moreover, because the above compounds are liquids,purification sometimes proves to be difficult. Further, the compounds ofSato '339 have stability issues. Thus, it would be desirable to be ableto generate compounds that are similar to the above compounds that canbe used effectively as starting materials for silicone-containingpolyester resins, polyamide resins and addition type polyimide resins,silane coupling agents, and coupling agents for polyimide resins, aswell as for plasticizers for vinyl chloride resins and similarcompounds, and for curing agents for epoxy resins that do not sufferfrom the same drawbacks as the compounds as disclosed in Sato '339.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to compounds, intermediates, compositions,and methods of making compounds and intermediates related to thecompounds of Formula I and/or Formula II and/or Formula III and/orFormula IV and/or Formula VI and/or Formula VII:

wherein A is a member selected from the group consisting of silicon,platinum, rhodium, boron, arsenic and palladium;

X and X′ are independently an aliphatic hydrocarbon chain or aromaticgroup which may be selected from one or more of the following alkyl,alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, wherein all of thealkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl groups maycontain one or more heteroatoms selected from the group consisting ofnitrogen, phosphorous, arsenic, antimony, bismuth, germanium, tin,oxygen, sulfur, selenium, tellurium, boron, aluminum, gallium, indium,germanium, and silicon, and wherein all of the alkyl, alkenyl, alkynyl,aryl, heteroaryl, heterocyclyl groups also may be optionally substitutedby one or more of the following, alkyl, alkenyl, alkynyl, aryl,heteroaryl, heterocyclyl, halo, cyano, oxo, hydroxy, mercapto, sulfonyl,sulfoxy, amino, imino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, nitroso, and thioxo. All of these substituentsmay, in turn, be optionally substituted with one or more substituentsindependently selected from the group consisting of halogen, hydroxy,cyano, carboxy, thiol, sulfo, nitro, nitroso, oxo, thioxo, and imino.

R₁, R₂, R₃, and R₄ are each independently selected from the groupconsisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl, halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy,amino, imino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, nitroso, and thioxo or

R₁ and R₂ together with the atoms connected to them or R₃ and R₄together with the atoms connected to them may form a spiro C₄₋₈cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; or

R₁ and R₃ together with the atoms connected to them or R₂ and R₄together with the atoms connected to them may form a C₃₋₁₀ cycloalkylgroup that may optionally contain one or more heteroatoms selected fromthe group consisting of nitrogen, phosphorous, arsenic, antimony,bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium, boron,aluminum, gallium, indium, germanium, and silicon.

Y is a counterion such as an alkali metal or other positively chargedion.

BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS

FIGS. 1A and 1B are S-trans and S-cis depictions, respectively of thesilatrane compound [(buta-1,3-dien-2-yl}silatrane] of the presentinvention as drawn from x-ray crystallography data.

FIGS. 2A and 2B are drawings of the catechol derived silicon compound{i.e., potassium [bis(1,2-benzenediolato)-1,3-butadien-2-yl-]silicate}of the present invention as drawn from x-ray crystallography data. FIG.2A contains two THF molecules and potassium whereas FIG. 2B has neitherpresent.

DETAILED DESCRIPTION OF THE INVENTION

The present invention generally relates to compounds, intermediates,compositions, and

methods of making compounds and intermediates related to the compoundsof Formula I and/or Formula II and/or Formula VII:

wherein the substituents are defined below. In an embodiment, Formula I,Formula II, and Formula VII are generated from the dienes shown inFormula III, Formula IV, and Formula VI,

respectively. Formula III, Formula IV, and Formula VI react with thedienophile shown in Formula V to generate the compounds as shown inFormulas I and II.

Alternatively any of the dienes of Figures III, IV, or VI can react withthe alkyne of figure VIII

in a Diels-Alder fashion to produce the corresponding alkenylenecompounds;wherein in the above Formulas I, II, III, IV, V, VI, VII and VIII;

A is a member selected from the group consisting of silicon, platinum,rhodium, boron, arsenic and palladium;

X and X′ are independently an aliphatic hydrocarbon chain or aromaticgroup which may be selected from one or more of the following alkyl,alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl, wherein all of thealkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl groups maycontain one or more heteroatoms selected from the group consisting ofnitrogen, phosphorous, arsenic, antimony, bismuth, germanium, tin,oxygen, sulfur, selenium, tellurium, boron, aluminum, gallium, indium,germanium, and silicon, and wherein all of the alkyl, alkenyl, alkynyl,aryl, heteroaryl, heterocyclyl groups also may be optionally substitutedby one or more of the following, alkyl, alkenyl, alkynyl, aryl,heteroaryl, heterocyclyl, halo, cyano, oxo, hydroxy, mercapto, sulfonyl,sulfoxy, amino, imino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, nitroso, and thioxo. All of these substituentsmay, in turn, be optionally substituted with one or more substituentsindependently selected from the group consisting of halogen, hydroxy,cyano, carboxy, thiol, sulfo, nitro, nitroso, oxo, thioxo, and imino.

R₁, R₂, R₃, and R₄ are each independently selected from the groupconsisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl, halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy,amino, imino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, nitroso, and thioxo or

R₁ and R₂ together with the atoms connected to them or R₃ and R₄together with the atoms connected to them may form a spiro C₄₋₈cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; or

R₁ and R₃ together with the atoms connected to them or R₂ and R₄together with the atoms connected to them may form a C₃₋₁₀ cycloalkylgroup that may optionally contain one or more heteroatoms selected fromthe group consisting of nitrogen, phosphorous, arsenic, antimony,bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium, boron,aluminum, gallium, indium, germanium, and silicon.

Y is a counterion such as an alkali metal. In an embodiment, Y ispotassium, sodium, tetrabutyl ammonium or other appropriate counterion.

It should be recognized that although the dienophile compounds ofFormula V are shown as an alkene, alkynyl dienophile compounds are alsocontemplated and therefore within the scope of the invention (whereineither one of R₁ and R₂ is present on one side of the carbon carbontriple bond and either one of R₃ and R₄ is present on the other side).The product that is generated is similar to the compounds shown inFormulas I and II but would be amended to be a cyclohexyl 1,4-dienylcompound (that is, to have either of R₁ and R₂ present on one side ofthe carbon carbon double bond and either one of R₃ and R₄ is present onthe other side).

Moreover, the compounds of Formulas I, II, III, IV, VI, and VII can alsobe used for polymerization reactions such as those that are present inTakenaka et al., Macromolecules, (1989), 22, pp. 1563-1567.

In an embodiment, the present invention is also directed to thesynthesis of the above compounds as represented by Formulas I, II, andVII above, using the starting materials shown in Scheme-60, whichgenerates intermediate 64.

Compound 32 can be used to make the corresponding dimethyl phenyl silanediene 32a.

Intermediate 64 can be used to generate a plurality of possiblecompounds. For example, compound 67 can be made using the belowscheme-61.

It should be recognized that any of a plurality of compounds can be usedinstead of compound 65. For example, the nitrogen in compound 65 can bereplaced by phosphorous or arsenic. Moreover, the lengths of the alkylchains in compound 65 can be varied to give any of a plurality ofcompounds. These compounds can then be reacted with a dienophile togenerate the compounds shown in Formula II above. The above scheme 61shows an example of the compounds that can be generated from Formula II.

Moreover, intermediate 64 can be reacted with a 1,2-dihydroxy benzene orother similar compounds to give phenyl containing compounds. An exampleof such a scheme is shown as scheme-62 to generate the bis-phenylsilicon containing diene 69.

Similar to Scheme 61, it should be recognized that any of a plurality ofcompounds

can be used instead of compound 68. For example, an alkyl chain may bepresent between the hydroxyl groups and the benzene ring. This willallow compounds to be generated from the 1,2-disubstituted benzenes,1,3-disubstituted benzenes, and 1,4-disubstituted benzenes. The dieneshown as compound 69 can then be reacted with a dienophile to generatecompounds such as those shown above in Formula II. This general reactionscheme is shown below in scheme 170

In this scheme, Ln represents ligands such as the catechol siliconderivative as shown in compound 69 in scheme-62 or the silatranefunctionality of compound 67 in scheme-61. Although the dienophile isshown as 1-phenyl-1H-pyrrole-2,5-dione, it should be recognized that anydienophile is contemplated and therefore within the scope of the presentinvention. Further, the silicon in the above reaction can be substitutedby any of the atoms that are listed as A in Formulas I and II above. Anexemplary embodiment of the catechol silicon derivative (Potassiumbis(1,2-benzenediolato)-(1,3-butadien-2-yl)silicate) reaction with1-phenyl-1H-pyrrole-2,5-dione is shown in below scheme 171:

Scheme 172 shows another exemplary embodiment of the catechol siliconderivative reaction with a different dienophile (i.e,3-methylfuran-2,5-dione).

Scheme 173 shows another exemplary embodiment of the catechol siliconderivative reaction with a different dienophile (i.e, methylpropiolate).

Scheme 174 shows another exemplary embodiment of the catechol siliconderivative reaction with a different dienophile (i.e, methyl2-methylacrylate).

Scheme 175 shows another exemplary embodiment of the catechol siliconderivative reaction with a different dienophile (i.e,1-phenyl-3,5-dimethyl-1H-pyrrole-2,5-dione):

Other dienophiles that can be used with the catechol silicon derivativein a Diels Alder reaction include Schemes 176-177:

One other dienophile that is contemplated is compound 10f

When compound 67 or 69 undergo a Diels Alder type reaction with compound8 (3-methylfuran-2,5-dione)

the regiochemistry of the product shows good selectivity. The generalproducts are shown as compounds 9 and 10

wherein Ln represents the ligands attached to the Si atoms as shown in67 and 69. The silatrane substituted diene (67) produced a 3.4:1 mixtureof para, meta regioisomers (9:10) in 78% isolated yield after heating to120° C. in THF for 48 h. The catechol silane substituted diene (69)reacted under slightly milder conditions (80° C. for 36 h) to produce a6.4:1 mixture of 9:10 in 92% isolated yield.

In contrast to the very good yields shown for a cycloaddition reactionwith the silicon compounds 67 (98% yield with compound 70a) and 69 (98%yield with compound 70a), when compound 64 is reacted with dienophilecompound 70a the yield was found to be 2%.

The compounds of Formula I, Formula II, Formula III, Formula IV, FormulaVI and Formula VII:

have as possibilities for A any of silicon, platinum, rhodium, boron,arsenic and palladium.

Any of the atoms that are possibilities for A can be present prior toundergoing the Diels Alder reaction. Alternatively, A can be silicon andan atom substitution reaction can be performed to substitute a differentatom for A. In an embodiment, in Formula III, A is silicon and X is notpresent (that is, the Si atom has three hydroxyl groups attached to it).

For example, the following scheme 59c shows that one means of generatingthe various atoms that are A is by substitution in a trans-metalationtype reaction. To substitute platinum or one of the above enumeratedatoms for the silicon atom, one can employ a transmetalation reaction.In scheme 59c, one can see this transmetalation reaction and should notethat this is a catalytic cycle.

Thus, it should be apparent that the silicon compound can be substitutedwith any of the above enumerated atoms for A. The advantages of thistransmetalation process is that it allows enhanced regio and stereoselectivity and a one-pot methodology can be employed.

The stable Pt(II) catalysts can be prepared by treating PtCl₂(dmso)₂with various ligands. A representative example for the synthesis of aPt(II) catalyst is outlined in Scheme-59d.

One means of generating terminal substituted silyl dienes is by aconversion from allenic acetates/allenic carboxylates. Alkoxysilyldienes (80) can be prepared by allylic substitution of the allenicacetates (77c, d) allenic carboxylates (77e, f) using(aminosilyl)lithiums (81c) which can be prepared in two steps using theprotocol shown in Scheme-68.

Alternatively, terminal substituted silyl dienes can also be preparedfrom halodienes. Alkoxysilyl dienes (80) can also be prepared by aS_(N)2′ reaction of the silylanions (81c) with halodienes (77a, b).During this coupling reaction, selective reductive elimination of thevinyl groups in the presence of aryl and alkyl groups may occur. SeeScheme-69.

Moreover, terminal substituted silyl dienes can also be prepared by thesilylation of halodienes. Alkoxy silyl dienes (83) can be prepared bysilylation of the halodienes (77a, b) with triethoxysilane in presenceof catalytic Rh(I) or Pd(0). See Scheme-70.

Intramolecular enyne cross-metathesis reactions of triethoxysilylalkyne(84) with olefins (85) in the presence of second-generation Grubbscatalyst (86) results in the stereoselective synthesis of(E)-1,3-disubstituted silylbutadienes (83) in moderate yields. SeeScheme-71.

Triethoxysilyl diene (83) can be prepared from the cross-coupling reactionof halodienes (77a, b) with triethoxychlorosilane (65) in the presenceof a catalytic amount of a transition metal, Pd(II) or Ni(II). SeeScheme-72.

It is contemplated that Rhodium-catalyzed asymmetric 1,4-addition oforganosilanes will work as shown below. Highly enantioselectiveasymmetric 1,4-addition reactions of trialkoxyorganosilanes withα,β-unsaturated carbonyl compounds (ketones, esters and amides) usingcatalytic chiral rhodium complexes are likely to work as shown inScheme-73.

Moreover, using similar methodologies as disclosed above, it is proposedthat the asymmetric catalysis reactions will work with the silyl dienesdisclosed in this application. A proposed mechanism is as shown inScheme-74.

Scheme-75 below shows a method for the synthesis of 2-halo-1-substituteddienes.

A means of synthesizing oxasilacyclodienes and their exo-selectiveDiels-Alder and cross-coupling reactions is shown below. The methodologyused to synthesize oxasilacyclodienes and their subsequent tandemDiels-Alder and cross-coupling reactions uses a catalytic pathway forexo-selective synthesis of substituted cyclohexenes (Scheme-59) or byfollowing the pathway for catalytic asymmetric 1,4-addition reactions(Scheme-74). Dienes may be prepared using either transition-metalcatalyzed hydrosilylation from respective enynols (as shown inScheme-76) or by base-catalyzed tandem reaction using carbonyl compoundsand alkynylsilanes (as shown in Scheme-77).

An embodiment of the present invention uses the dienes 20 and 23 inscheme 78 as starting materials to undergo the Diels Alder reaction withthe dienophile compounds of Formula V. Scheme 78 shows how dienecompounds 20 and 23 can be synthesized.

Another embodiment of the present invention are compounds that aresimilar to 26a

which can be made by a synthetic scheme as shown in scheme 79.

The diene that is generated in the above scheme can be reacted with adienophile. For example compound 26a will undergo reaction with adienophile in a Diels Alder type fashion to generate compounds such ascompound 27a. It should be recognized that any of the above compounds orcompounds similar to those from Scheme 79 will undergo this Diels Aldertype reaction to generate the corresponding product. See scheme 80 foran example.

Although all of the above reactions are shown with a separate selfcontained dienophile, it should be recognized that intramolecularreactions are contemplated and therefore within the scope of the presentinvention. For example, a compound such as 31 might be employed toundergo a Diels Alder type intramolecular reaction.

This is a possible route to generating polycyclic compounds that may endup being useful for one or more of the purposes discussed elsewhere inthis written description.

The compounds of Formulas I, II, and VII may also prove to be usefulstarting materials to generate other compounds. For example, the Acontaining substituent from the cyclohexene ring in the compounds ofFormulas I and II

can be replaced by a group that has carbon attached to the cyclohexenering. For example, when compound 101 is reacted with dienophile 1(containing an electron withdrawing group), and then subsequentlyreacted with an alkyl halide, the silicon containing substitutent isremoved. See scheme 81.

Experimental General Experimental Protocol

All ¹H NMR spectra were recorded by using a Bruker Avance 500 MHzspectrometer and Bruker Avance 300 MHz spectrometer operating at 500.13MHz and 300.13 MHz respectively. ¹³C NMR spectra were recorded on aBruker Avance 300 MHz spectrometer and Bruker Avance 500 MHzspectrometer operating at 75.48 MHz and 125.77 MHz respectively.Chemical shifts were reported in parts per million (δ) relative totetramethylsilane (TMS) or chloroform (CDCl3). Coupling constants (Jvalues) were reported in hertz (Hz), and spin multiplicities wereindicated by the following symbols: s (singlet), d (doublet), t(triplet), q (quartet), p (pentet), s (sixtet), h (heptet) and m(multiplet).

All elemental analyses were carried out by Atlantic Microlabs Inc., GA.High resolution

mass spectrometric (HRMS) analyses were carried out at the Duke MassSpectrometric Facility,

Durham, N.C. and Mass Spectrometry Center at UNC-Chapel Hill, N.C. Flashchromatography was performed using thick-walled glass chromatographycolumns and “Ultrapure” silica gel (Silicycle Ind., Canada, 40-63 μm).Vacuum filtrations were carried out with the aid of microanalysis vacuumfilter apparatus and Millipore filter membranes.

All reactions were carried out under an inert atmosphere unlessotherwise noted. Tetrahydrofuran, dimethylformamide and methylenechloride were purchased from Fischer Scientific in the form of solventkegs and distilled by using the centrally located solvent dispensingsystem developed by J. C. Meyer. Hexanes were distilled over CaH₂ beforeuse. Silyl reagents were either purchased from Sigma-Aldrich or GelestInc. Deuterated solvents were purchased from Cambridge Isotopes and usedas received. All other chemicals were purchased from Sigma-Aldrich andused as received.

General Procedure for Syntheses of 2-Silyl Substituted (Conjugated)Dienes. 2-Silyl substituted-1,3-butadienes and terminally substituted2-silyl-1,3-dienes can be prepared efficiently by nucleophilic additionof the concerned Grignard reagents either in hot reaction conditions(Method-A) or in cold reaction conditions (reverse addition) (Method-B)as described below.Method-A. Silyl diene was prepared in an oven-dried 100 mL 2-neckround-bottom flask equipped with a magnetic stir bar, addition funneland reflux condenser, which was charged with magnesium (1.6 eq) followedby the addition of dibromoethane (11.0 mol %) in THF (5 mL). Afterstirring ˜ca. 5 min (initiation of magnesium activation can be noticedby its silver color and ethane gas liberation), 3.0 mol % of anhydrousZnCl₂ in THF (5 mL) was added. This mixture was added with additionalTHF (30 mL) and resulted in a whitish-grey solution which was brought togentle reflux over a period of 15 min. Chloroprene (in 50% xylenes) (1.0eq) and dibromoethane (23.0 mol %) in THF (25 mL) was added drop-wise tothe refluxing reaction mixture over 30 min. After the addition,refluxing was continued for another 45 min. The greenish-grey coloredGrignard solution was transferred by canula into a 250 mL, one-neckround-bottomed flask containing triethoxychlorosilane (0.95 eq) in THF(25 mL) at room temperature. The reaction mixture was refluxed (1 h),poured into 0.5M HCl solution (100 mL) and extracted with pentane (2×75mL). The combined colorless clear organic layers were washedsuccessively with 0.5M HCl (75 mL) and water (2×100 mL). After dryingover MgSO₄, the solvent was removed under reduced pressure to yield2-substituted silyl diene with xylenes as a colorless liquid. Thiscompound was subjected for fractional vacuum distillation to removexylenes and then purified by flash chromatography. Method-B. Substitutedsilyl dienes were prepared according to an analogous procedure withslight modifications. Magnesium turnings (3.0 eq) and iodine (4.0 mol %)were taken into a 2-neck, 100 mL round-bottomed flask fitted refluxcondenser, additional funnel and stir-bar. After adding THF (2.0 mL) andstirring for ca ˜2 min, dibromoethane (15 mol %) in THF (5.0 mL) wasadded at room temperature. After cessation of ethane gas, the reactionflask was cooled to 0° C. using an ice-bath, and stirring continued for10 min. to which silylchloride (1.3 eq) in THF (10 mL) was addeddropwise over 15 min. followed by dropwise addition of a mixture of1-[(E)-3-bromobuta-1,3-dienyl]benzene (1.0 eq) and dibromoethane (30 mol%) in THF (20 mL) over a period of 45 min. After the addition of ahalodiene, stirring was continued for 1 h at 0° C. and, then at roomtemperature overnight. The reaction mixture was filtered through a padof celite made with diethyl ether and then quenched with 0.6 M HCl (50mL), extracted with diethyl ether (3×30 mL). Thr combined organic layerswere washed with brine solution (2×50 mL), dried over MgSO₄ andvolatiles were removed. The crude residue of the reaction mixture waspurified by flash chromatography resulting in the silyl diene in almostquantitative yields.General Procedure for Synthesis of Enynylsilane.

Enynylsilanes were prepared according to a procedure similar to thatreported by Maifeld et al. (Unusual Tandem Alkynylation andtrans-Hydrosilylation To Form Oxasilacyclopentenes; Org. Lett. 2005,7(22), 4995-98) To a stirring colorless clear solution of enyne (1.05eq) in THF (20 mL) at −78° C., nBuLi (1.10 eq, 1.6M solution in hexanes)was added in ˜ca. 15 min. The yellow-brown, clear reaction mixture wasstirred for 15 min. at this temperature, then chlorosilane (1.0 eq)taken in THF (15 mL) was added dropwise over a period of 15 min. Afterstirring at this temperature for 30 min, the white cloudy reactionmixture was brought to room temperature and stirring continuedovernight. The white thick reaction mixture was diluted with Et₂O (50mL) and quenched with aq. NH₄Cl (100 mL) solution. Aqueous layersextracted with Et₂O (2×25 mL) and the combined organic layers werewashed with brine (100 mL), and dried over MgSO₄. After removal ofvolatiles, the crude product was purified by chromatography.

Synthesis of 2-triethoxysilyl-1,3-butadiene (2)

An oven-dried 100 mL 2-neck round-bottom flask equipped with a magneticstir bar, addition funnel and reflux condenser was charged withmagnesium (1.0 g, 0.041 mol) followed by the addition of dibromoethane(250 μL, 11.0 mol %) in THF (5 mL). After stirring ˜ca. 5 min(initiation of magnesium activation can be noticed by its silver colorand ethane gas liberation), 3.0 mol % of anhydrous ZnCl₂ (1.231 mmol,0.168 g) in THF (5 mL) was added. This mixture was added with additionalTHF (30 mL) and resulted in a whitish-grey solution which was brought togentle reflux. Chloroprene in 50% xylenes (5.04 mL, 0.026 mol) anddibromoethane (520 μL, 23.0 mol %) in THF (25 mL) was added dropwiseover a 30 min. with the aid of an addition funnel. After the addition,refluxing was further continued for another 45 min. The greenish-greycolored Grignard solution was transferred by canula in to a 250 mL,one-neck round-bottomed flask containing triethoxychlorosilane (5.0 mL,0.025 mol) in THF (25 mL) at room temperature. The reaction mixture wasrefluxed (1 h), poured into 0.5M HCl solution (100 mL) and extractedwith pentane (2×75 mL). The combined colorless clear organic layers werewashed successively with 0.5M HCl (75 mL) and water (2×100 mL). Afterdrying over MgSO₄, the solvent was removed under reduced pressure toyield compound 32 with xylenes (1.66:1.0) as a colorless liquid. Thiscompound can be used in the ligand exchange reactions to make compounds3 and 4 or can be purified by fractional distillation under controlledpressure. The title compound (2) distills as a colorless liquid (4.55 g,0.021 mmol, 84.7%) after the xylenes (55° C.-60° C., 4 mm). ¹H NMR (300MHz, CDCl₃) δ 6.45 (dd, J=17.5, 10.7 Hz, 1H, H-3), 5.90 (d, J=3.4 Hz,1H, H-1), 5.81 (d, J=3.4 Hz, 1H, H-1), 5.54 (d, J=17.5 Hz, 1H,H-4_(trans)), 5.14 (d, J=10.7 Hz, 1H, H-4_(cis)), 3.84 (q, J=7.0 Hz, 6H,H-5), 1.23 (t, J=7.0 Hz, 9H, H-6); ¹³C NMR (300 MHz, CDCl₃) δ 141.1(C-2), 140.4 (C-3), 133.4 (C-1), 117.9 (C-4), 58.6 (C-5), 18.1 (C-6);Anal. calcd for C₁₀H₂₀O₃Si: C, 55.53; H, 9.33. Found: C, 55.93; H, 9.09.

Synthesis of (buta-1,3-dien-2-yl)silatrane (3)

A one neck round bottomed flask (100 mL) fitted with a reflux condenserwas charged with THF solution (30 mL). To this flask, triethanolamine(0.620 g, 4.156 mmol), compound 2 (1.0 g, 4.647 mmol) and catalyticamount of KOH powder (5 mol %, 0.032 g, 0.058 mmol) were addedsuccessively. Under refluxing for 15 min. the reaction mixture turnsclear orange-brown and then the reaction mixture was cooled to roomtemperature and pentane (100 mL) was added to precipitate the product.The light yellow solid was filtered and washed with ice-cold pentane(3×25 mL) to produce compound 3 (0.857 g, 3.774 mmol, 90.8%) as a yellowfluffy powder. This compound was used to carry-out the cycloadditionreactions without any further purification. X-ray quality crystals wereprepared by dual solvent crystallization technique where the compound 3was first dissolved in dichloroethane and then cyclohexane was added forslow diffusion to produce 3 as white needles: m.p (neat) 104-106° C.;NMR (300 MHz, CDCl₃) δ 6.51 (dd, J=17.5, 10.7 Hz, 1H, H-3), 5.74 (d,J=4.5 Hz, 1H, H-1), 5.64 (d, J=4.5 Hz, 1H, H-1), 5.42 (dd, J=17.5, 2.3Hz, 1H, H-4_(trans)), 5.03 (dd, J=10.7, 2.3 Hz, 1H, H-4_(cis)), 3.86 (t,J=5.8 Hz, 6H, H-5/6), 2.86 (t, J=5.8 Hz, 6H, H-5/6); ¹³C NMR (300 MHz,CDCl₃) δ 149.6 (C-2), 143.0 (C-3), 128.3 (C-1), 115.1 (C-4), 57.8(C-5/6), 51.3 (C-5/6); HRMS calcd for C₁₀H₁₇O₃SiN (M⁺) 227.0978. found227.0979. Anal. calcd for C₁₀H₁₇O₃SiN: C, 52.84; H, 7.54. Found: C,53.37; H, 7.67.

Synthesis of potassiumbis(1,2-benzenediolato)-(1,3-butadien-2-yl)silicate (4)

Catechol (5.115 g, 0.046 mol) was dissolved in THF (60 mL) followed bythe addition of compound 2 (5.0 g, 0.023 mol) and KOH powder (1.30 g,0.023 mol) successively. The reaction mixture was refluxed for one hourand the colorless solution turned to clear dark orange. After reflux,the reaction mixture was brought to room temperature, filtered to removesolid particles and pentane was added to precipitate the product as apale grayish white powder (7.772 g, 0.023 mol, 99.5%). Purification ofthe title compound was carried out by dissolving the product ( . . . g)in minimum quantity of hot THF, filtration and solidification by coolingthe flask at −40° C. for 1 h (% of recovery). For crystallographicstudies, recrystallization was carried out by dissolving the compound 4taken up in a small test tube with small quantity of hot THF andcyclohexane was added carefully along the walls. This test tube was leftat room temperature for slow diffusion and the crystals grew out at thejunction of the two solvents as white needles: m.p (neat) 242° C. (dec);¹H NMR (300 MHz, DMSO) δ 6.49-6.60 (m, 4H, H-6/7), 6.40-6.49 (m, 4H,H-6/7), 6.20 (dd, J=17.5, 10.6 Hz, 1H, H-3), 5.29 (dd, J=17.5, 2.3 Hz,1H, H-4_(trans)), 5.28 (d, J=4.1 Hz, 1H, H-1), 5.18 (d, J=4.1 Hz, 1H,H-1), 4.77 (dd, J=10.6, 2.3 Hz, 1H, H-4_(cis)); ¹³C NMR (300 MHz, DMSO)δ 151.3 (C-2), 150.3 (C-5), 142.2 (C-3), 123.5 (C-1), 117.3 (C-6/7),114.5 (C-4), 109.7 (C-6/7). Anal. calcd for C₁₆H₁₃O₄SiK: C, 57.14; H,3.90. Found: C, 56.96; H, 3.84.

General procedure for Diels-Alder reactions: The diene was dissolved inTHF (2 mL) in a thick walled micro wave tube charged with a ministir-bar. After purging with nitrogen for 2 min., dienophile was addedand the tube was closed with an aluminum seal and the reaction was runwith continuous stirring at a stipulated time and temperature. Themicrowave tube was then brought to room temperature and the seal wasbroken.

Synthesis of cycloadduct shown below (6): Diene-3 (0.050 g, 0.220 mmol)as shown above and N-phenylmaleimide (0.080 g, 0.462 mmol) was usedaccording to the general procedure for the cycloaddition reaction. Afterstirring 30 min. at room temperature, the reaction mixture was filteredthrough a cotton plug and addition of pentane (5 mL) to the filtrateresulted in cycloadduct (6) as white crystalline powder (0.086 g, 0.215mmol, 97.8%): m.p (neat) 170-172° C.; ¹H NMR (500 MHz, CDCl₃) δ 7.41 (t,J=7.8 Hz, 2H, H-8), 7.33 (t, J=7.4 Hz, 1H, H-9), 7.29 (d, J=7.4 Hz, 2H,H-7), 6.43 (t, J=4.1 Hz, 1H, H-2), 3.77 (t, J=6.0 Hz, 6H, H-13),2.87-3.19 (m, 2H, H-4, 11), 2.81 (t, J=6.0 Hz, 6H, H-14), 2.66 (dd,J=14.8, 4.0 Hz, 1H, H-12), 2.44-2.59 (m, 2H, H-3, 12), 2.28-2.40 (m, 1H,H-3); ¹³C NMR (300 MHz, CDCl₃) δ 179.7 (C-5/10), 179.6 (C-5/10), 142.8(C-1), 134.3 (C-2), 132.5 (C-6), 128.8 (C-8), 128.1 (C-9), 126.8 (C-7),57.5 (C-13), 51.0 (C-14), 39.81 (C-4/11), 39.76 (C-4/11), 27.6 (C-12),24.4 (C-3); Anal. calcd for C₂₀H₂₄N₂O₅Si: C, 59.98; H, 6.04. Found: C,60.34; H, 6.43.

Synthesis of cycloadduct (7) shown below: Diene-4 (0.300 g, 0.893 mmol)and N-phenylmaleimide (0.246 g, 1.421 mmol) was used in thecycloaddition reaction according to the general procedure. Afterstirring for 30 min. at room temperature, the product was seenprecipitating out as a white solid. Further precipitation was carriedout by adding pentane (5.0 mL) and quick filtration yielded cycloadduct(7) as a white fluffy powder (0.450 g, 0.884 mmol, 99.0%): m.p (neat)310° C. (dec); ¹H NMR (500 MHz, DMSO) δ 7.34-7.46 (m, 3H, H-8, 9),6.85-6.97 (m, 2H, H-7), 6.54-6.64 (m, 4H, H-15), 6.45-6.54 (m, 4H,H-14), 6.23 (bs, 1H, H-2), 3.08-3.19 (m, 1H, H-11), 2.98-3.07 (m, 1H,H-4), 2.69 (dd, J=14.9, 3.4 Hz, 1H, H-12), 2.33 (ddd, J=15.1, 5.9, 4.0Hz, 1H, H-3), 2.05-2.17 (m, 2H, H-3, 12); ¹³C NMR (500 MHz, DMSO) δ179.4 (C-5), 178.9 (C-10), 150.5 (C-13), 150.2 (C-13), 142.8 (C-1),135.5 (C-2), 132.6 (C-6), 128.6 (C-8), 127.9 (C-9), 127.2 (C-7), 117.4(C-15), 117.1 (C-15), 109.8 (C-14), 109.6 (C-14), 39.1 (C-4/11), 39.0(C-4/11), 26.9 (C-12), 24.1 (C-3); Anal. calcd for C₂₆H₂₀O₆SiNK: C,61.29; H, 3.96. Found: C, 61.03; H, 4.35. The unreacted dienophile(0.089 g, 0.514 mmol, 97.4%) was recovered after removal of the organicsby using the rotovap.

Synthesis of cycloadducts shown below: Diene-3 (0.271 g, 1.192 mmol) andcitraconic anhydride (0.163 g, 1.454 mmol) was dissolved in 5 mL of THFtaken in a seal tube and was heated at 120° C. over a period of 48 h.After which the reaction mixture brought to room temperature,precipitated with pentane (10 mL) followed by vacuum filtration resultedthe cycloadduct (9, 10) as white crystalline solid (0.314 g, 0.925 mmol,77.5%). Major Isomer: ¹H NMR (500 MHz, C₆D₆): δ 6.63-6.82 (m, 1H, H-2),3.32 (t, J=6.0 Hz, 6H, H-10), 3.20 (d, J=14.0 Hz, 1H, H-8), 2.44 (dd,J=15.0, 6.2 Hz, 1H, H-3), 2.21-2.34 (m, 2H, H-7, 8), 1.83 (t, J=6.0 Hz,6H, H-11), 1.55 (ddd, J=15.0, 3.7, 1.8 Hz, 1H, H-3), 0.78 (s, 3H, H-9);¹³C NMR (300 MHz, C₆D₆) δ 178.2 (C-), 174.2 (C-), 173.7 (C-), 143.81(C-), 143.77 (C-), 133.5 (C-2), 57.5 (C-10), 50.6 (C-11), 47.45 (C-7),46.0 (C-), 33.1 (C-3), 28.0 (C-8), 23.9 (C-9); Minor Isomer: ¹H NMR (500MHz, C₆D₆): δ 6.63-6.82 (m, 1H, H-2), 3.30 (t, J=6.0 Hz, 6H, H-10), 3.08(d, J=15.0 Hz, 1H, H-8), 2.53 (ddd, J=15.7, 6.2, 2.7 Hz, 1H, H-3), 2.15(dd, J=6.7, 2.7 Hz, 1H, H-4), 2.03 (dt, J=15.0, 2.2 Hz, 1H, H-8), 1.81(t, J=6.0 Hz, 6H, H-11), 1.72-1.79 (m, 1H, H-3), 0.97 (s, 3H, H-9); ¹³CNMR (300 MHz, C₆D₆) δ 178.2 (C-), 174.2 (C-), 173.7 (C-), 143.81 (C-),143.77 (C-), 133.0 (C-2), 57.5 (C-10), 50.6 (C-11), 47.50 (C-4), 46.0(C-), 36.9 (C-8), 24.2 (C-3), 23.6 (C-9); Anal. calcd for C₁₅H₂₁NO₆Si:C, 53.08; H, 6.24. Found: C, ; H, . Regio isomer ratio 2.0:1.0 (based on¹H NMR)

General procedure for cross-coupling reaction by using cycloadduct-6:Cross-coupling reaction was carried out according to the reportedliterature procedure by using 6 (0.155 g, 0.387 mmol), Pd(OAc)₂ (0.024g, 0.041 mmol), PPh₃ (0.024 g, 0.092 mmol), Iodobenzene (0.083 g, 0.407mmol) were dissolved in DMF (10 mL). After stirring to homogenate thereaction mixture, TBAF (0.118 g, 0.374 mmol) dissolved in THF (5.0 mL)was added and the reaction flask was purged with N₂, and heated for 2 hat 90° C. After which the reaction mixture was quenched with water (50mL), and extracted with Et₂O (4×50 mL). The combined organic layers wereagain washed with water (2×75 mL), dried over MgSO₄ and volatiles wereremoved by rotovap. The brown colored oily crude reaction mixture wassubjected to flash chromatography to yield the cross-coupled product aswhite solid (0.098 g, 0.323 mmol, 83.4%): m.p (neat) 122-124° C.; R_(f)0.27 (hexanes/diethyl ether, 1:1); ¹H NMR (500 MHz, CDCl₃) δ 7.38-7.45(m, 2H, H-8), 7.30-7.38 (m, 5H), 7.24-7.29 (m, 1H), 7.10-7.20 (m, 2H),6.15-6.27 (m, 1H, H-2), 3.44 (ddd, J=9.5, 6.9, 2.5 Hz, 1H, H-11), 3.35(ddd, J=9.5, 6.9, 2.5 Hz, 1H, H-4), 3.26 (dd, J=15.1, 2.5 Hz, 1H, H-12),2.95 (ddd, J=15.5, 6.9, 2.5 Hz, 1H, H-3), 2.64 (ddt, J=15.1, 6.9, 2.5Hz, 1H, H-12), 2.40-2.50 (m, 1H, H-3); ¹³C NMR (500 MHz, CDCl₃) δ 179.1(C-5), 178.9 (C-10), 140.4 (C-13), 140.1 (C-1), 131.2 (C-6), 129.1(C-8), 128.58 (C-14/15/16), 128.56 (C-14/15/16), 127.5 (C-9), 126.4(C-7), 125.5 (C-14/15/16), 123.2 (C-2), 40.1 (C-11), 39.5 (C-4), 27.6(C-12), 25.3 (C-3); Anal. calcd for C₂₀H₁₇O₂N: C, 79.19; H, 5.65. Found:C, 77.88; H, 5.76.

Dimethyl(pent-3-en-1-ynyl)silane

The general procedure mentioned above using pent-3-en-1-yne (3.142 g,47.52 mmol), nBuLi (32.0 mL, 51.2 mmol), and dimethylchlorosilane (4.34g, 45.9 mmol) produced the compound as a colorless clear liquid afterpurification by using flash chromatography (5.542 g, 44.67 mmol, 94%):Rf 0.39 (100% hexanes); Major isomer(trans): ¹H NMR (500 MHz, CDCl₃) δ6.22 (dq, J=15.9, 6.8 Hz, 1H, H-4), 5.50-5.54 (m, 1H, H-3), 4.16 (h,J=3.8 Hz, 1H, H-6), 1.77 (dd, J=6.8, 1.8 Hz, 3H, H-5), 0.23 (dd, J=3.8,1.3 Hz, 6H, H-7); ¹³C NMR (300 MHz, CDCl₃) δ 141.6 (C-4), 110.7 (C-3),105.4 (C-2), 89.3 (C-1), 18.6 (C-5), −3.0 (C-7); Minor Isomer(cis): ¹HNMR (500 MHz, CDCl₃) δ 6.04 (dq, J=10.8, 6.8 Hz, 1H, H-4), 5.46-5.50 (m,1H, H-3), 4.20 (h, J=3.8 Hz, 1H, H-6), 1.89 (dd, J=6.8, 1.8 Hz, 3H,H-5), 0.26 (dd, J=3.8, 1.3 Hz, 6H, H-7); ¹³C NMR (300 MHz, CDCl₃) δ140.5 (C-4), 110.0 (C-3), 103.2 (C-2), 95.8 (C-1), 16.1 (C-5), −2.9(C-7); HRMS calcd for C₁₁H₂₀Si (M+) 124.0708. found 124.0708. Regioisomer ratio 1.0:1.2 (cis to trans, based on ¹H NMR).

Methyl(phenyl)(pent-3-en-1-ynyl)silane

Pent-3-en-1-yne (1.032 g, 15.61 mmol), nBuLi (10.2 mL, 16.32 mmol) andmethyl(phenyl)chlorosilane (2.22 g, 14.18 mmol) produced a crude productwhich was subjected to column chromatographic purification yielded thecompound as a colorless, clear liquid (2.66 g, 14.29 mmol, 96.0%): Rf0.33 (100% hexanes); Major isomer(cis): ¹H NMR (500 MHz, CDCl₃) δ7.65-7.77 (m, 2H, H-9), 7.37-7.50 (m, 3H, H-10, 11), 6.13 (dq, J=10.9,6.9 Hz, 1H, H-4), 5.61-5.65 (m, 1H, H-3), 4.80 (q, J=3.7 Hz, 1H, H-6),1.98 (dd, J=6.9, 1.9 Hz, 3H, H-5), 0.57 (d, J=3.7 Hz, 3H, H-7); ¹³C NMR(300 MHz, CDCl₃) δ 141.2 (C-4), 134.3 (C-9), 133.9 (C-8), 129.7 (C-11),128.0 (C-10), 110.0 (C-3), 104.9 (C-2), 93.6 (C-1), 16.2 (C-5), −3.5(C-7), −3.6 (C-7); Minor isomer(trans) (diagnostic peaks): ¹H NMR (500MHz, CDCl₃) δ 6.35 (dq, J=15.7, 6.9 Hz, 1H, H-4), 5.58-5.61 (m, 1H,H-3), 4.75 (q, J=3.7 Hz, 1H, H-6), 1.84 (dd, J=6.9, 1.9 Hz, 3H, H-5),0.54 (d, J=3.7 Hz, 3H, H-7); ¹³C NMR (300 MHz, CDCl₃) δ 142.2 (C-4),110.6 (C-3), 107.1 (C-2), 87.1 (C-1), 18.7 (C-5); Anal. calcd forC₁₂H₁₄Si: C, 77.35; H, 7.57. Found: C, 77.09; H, 7.68. Regio isomerratio 1.2:1.0 (cis to trans, based on ¹H NMR).

General Procedure for the Synthesis of Propargylic Alcohols.

Propargylic alcohols were prepared by the addition of lithium acetylideto the corresponding aldehyde as follows. To a solution of alkyne (1.0eq) taken in THF (75 mL) at −78° C. was added nBuLi (1.1 eq, 1.6Msolution in hexanes) in ˜ca. 30 min. The resulting clear orange solutionwas raised to 0° C. and stirred for an additional 1 h and the flask wasagain cooled back to −78° C. After the addition of the respectiveelectrophile (1.25 eq), stirring was continued overnight at roomtemperature followed by quenching with saturated aqueous NH₄Cl (100 mL).Aqueous layers were extracted with Et₂O (3×50 mL), followed by washingof combined organics with saturated aqueous NaCl solution (100 mL).Solvent was removed by rotary evaporation and the crude product wasfurther purified by flash chromatography.

4-Methyl-1-phenylpent-4-en-2-yn-1-ol

2-Methylbut-1-en-3-yne (3.45 g, 52.19 mmol), nBuLi (36.0 mL, 57.6 mmol)and benzaldehyde (6.642 g, 62.63 mmol) were used according to thegeneral method mentioned above. Purification of the resulting clearyellow-brown crude product yielded the pure product as a clearyellow-brown oil (8.442 g, 49.02 mmol, 93.9%): Rf 0.72 (hexanes/Et₂O,4:1); ¹H NMR (300 MHz, CDCl₃) δ 7.49-7.69 (m, 2H, H-8), 7.30-7.49 (m,3H, H-9, 10), 5.58 (d, J=6.2 Hz, 1H, H-1), 5.37 (bs, 1H, H-5), 5.28 (p,J=1.5 Hz, 1H, H-5), 2.43 (d; J=6.2 Hz, 1H, —OH), 1.93 (bs, 3H, H-10);¹³C NMR (300 MHz, CDCl₃) δ 140.6 (C-7), 128.6 (C-9), 128.3 (C-10), 126.6(C-8), 126.1 (C-4), 126.6 (C-5), 87.8 (C-2/3), 87.7 (C-2/3), 64.9 (C-1),23.3 (C-6); HRMS calcd for C₁₂H₁₂O (M+) 172.0888. found 172.0885.

2,5-Dimethylhex-5-en-3-yn-2-ol

2-Methylbut-1-en-3-yne (3.45 g, 52.19 mmol), nBuLi (36.0 mL, 57.6 mmol)and acetone (3.89 g, 66.96 mmol) produced a brown crude reaction mixturewhich upon purification by flash chromatography yielded the pure productas a clear yellow oil (2.232 g, 17.97 mmol, 33.4%): Rf 0.22(hexanes/Et₂O, 4:1); ¹H NMR (500 MHz, CDCl₃) δ 5.21 (s, 1H, H-6), 5.15(s, 1H, H-6), 2.48-2.93 (bs, 1H, —OH), 1.82 (as, 3H, H-7), 1.49 (as, 6H,H-1, 8); ¹³C NMR (300 MHz, CDCl₃) δ 126.3 (C-5), 121.7 (C-6), 92.8(C-3), 83.2 (C-4), 65.4 (C-2), 31.4 (C-1, 8), 23.4 (C-7); HRMS calcd forC₈H₁₂O (M+) 124.0888. found 124.0885.

3,6-Dimethylhepta-1,6-dien-4-yn-3-ol

The title compound was prepared according to the general method above byusing 2-methylbut-1-en-3-yne (1.725 g, 26.09 mmol), nBuLi (18.0 mL, 28.8mmol) and but-3-en-2-one (2.194 g, 31.30 mmol). Crude product waspurified by flash chromatography (2.229 g, 16.37 mmol, 62.7%): Rf 0.28(hexanes/Et2O, 4:1); ¹H NMR (300 MHz, CDCl₃) δ 6.00 (dd, J=17.1, 10.2Hz, 1H, H-2), 5.49 (dd, J=17.1, 0.7 Hz, 1H, H-1trans), 5.25-5.32 (m, 1H,H-7), 5.18-5.25 (m, 1H, H-7), 5.11 (dd, J=10.2, 0.7 Hz, 1H, H-1 cis),2.24 (s, 1H, —OH), 1.88 (as, 3H, H-8), 1.56 (s, 3H, H-9); 13C NMR (300MHz, CDCl₃) δ 142.0 (C-2), 126.2 (C-6), 122.1 (C-7), 113.5 (C-1), 89.9(C-4/5), 85.9 (C-4/5), 68.5 (C-3), 29.9 (C-9), 23.4 (C-8); HRMS calcdfor C₉H₁₃O (M+H)+ 137.0966. found 137.0984.

3-Cyclohexenyl-1-phenylprop-2-yn-1-ol [6f]

1-Ethynylcyclohex-1-ene (1.987 g, 18.71 mmol), ^(n)butyllithium (14 mL,1.6M in hexanes, 22.4 mmol) and benzaldehyde (2.43 g, 22.92 mmol)produced a yellow-brown crude reaction mixture which upon purificationby flash chromatography yielded the pure product OH as a light yellowcolored oily substance (3.84 g, 18.09 mmol, 96.7%): R_(f)0.47(hexanes/Et₂O, 2:1). Spectral data is consistent with earlier reporteddata.

General Procedure for Syntheses of Siloxy Substituted Enynes (7a, 7c-esee below). Siloxy substituted enynes were prepared by the followingmethod analogous to reported procedures. For example, Alkenynol (1.0eq), dimethylaminopyridine (10 mol %), and triethylamine (1.01 eq) wereadded at 0° C. to a 250 mL, single-neck round bottom flask containinghexanes (100 mL). The flask was charged with a stirbar and an additionfunnel. After stirring, chlorosilane (taken in hexanes (10 mL) was addeddropwise over a period of 20 min. during which the reaction mixtureslowly turns to a cloudy white suspension. Later the reaction mixturewas brought to ambient temperature and stirring continued overnight. Thethick white reaction mixture was filtered through a pad of silica usinga sintered funnel, and the silica pad was washed with hexanes (2×20 mL).After removal of volatiles, the crude product was purified using flashchromatography.

(4-Methylpent-4-en-2-ynyloxy)diisopropylsilane [7a]

4-Methylpent-4-en-2-yn-1-ol (2.0 g, 20.80 mmol), dimethylaminopyridine(0.252 g, 2.1 mmol), triethylamine (2.126 g, 21.01 mmol) anddiisopropylchlorosilane (3.135 g, 20.80 mmol) were used according to thegeneral procedure described above. The resulting clear, light yellowcolored crude compound was purified by flash chromatography to yieldpure product (3.914 g, 18.62 mmol, 89.5%) as clear colorless solution:R_(f) 0.82 (hexanes/Et₂O, 9:1); ¹H NMR (500 MHz, CDCl₃) δ 5.28 (bs, 1H,H-5), 5.22 (bs, 1H, H-5), 4.49 (s, 1H, H-1), 4.21 (s, 1H, H-7), 1.88 (s,3H, H-6), 0.74-1.37 (m, 14H, H-8, 9); ¹³C NMR (300 MHz, CDCl₃) δ 126.5(C-4), 121.8 (C-5), 86.5 (C-3), 86.3 (C-2), 54.3 (C-1), 23.2 (C-6), 17.3(C-9), 17.2 (C-9), 12.3 (C-8); Anal. calcd for C₁₂H₂₂OSi: C, 68.51; H,10.54. Found: C, 68.32; H, 10.73.

(2,5-Dimethylhex-5-en-3-yn-2-yloxy)diisopropylsilane [7c]

2,5-Dimethylhex-5-en-3-yn-2-ol (6c) (1.772 g, 14.27 mmol), triethylamine(1.690 g, 15.34 mmol), dimethylaminopyridine (0.180 g, 1.50 mmol) anddiisopropylchlorosilane (1.918 g, 12.73 mmol) produced 7c as a colorlessclear oil (2.232 g, 9.36 mmol, 73.5%) after purification by flashchromatography: R_(f) 0.90 (hexanes/Et₂O, 4:1); ¹H NMR (500 MHz, CDCl₃)δ 5.24 (as, J=0.9 Hz, 1H, H-6), 5.19 (p, J=1.4 Hz, 1H, H-6), 4.38 (at,J=1.4 Hz, 1H, H-9), 1.87 (t, J=1.4 Hz, 3H, H-7), 1.52 (s, 6H, H-1, 8),1.01-1.07 (m, 14H, H-10, 11); ¹³C NMR (300 MHz, CDCl₃) δ 126.6 (C-5),121.2 (C-6), 92.9 (C-3), 84.2 (C-4), 67.4 (C-2), 32.4 (C-1, 8), 23.4(C-7), 17.6 (C-11), 17.5 (C-11), 12.6 (C-10); HRMS calcd for C₁₄H₂₇OSi(M+H)⁺ 239.1831. found 239.1819.

(3,6-Dimethylhepta-1,6-dien-4-yn-3-yloxy)diisopropylsilane [7d]

3,6-Dimethylhepta-1,6-dien-4-yn-3-ol (6d) (1.523 g, 11.18 mmol),triethylamine (1.2 g, 11.86 mmol), dimethylaminopyridine (0.153 g, 1.275mmol) and diisopropylchlorosilane (1.657 g, 10.99 mmol) were usedaccording to the general procedure. The brown, clear crude product waspurified by column chromatography to produce the title compound (7d) asa clear colorless solution (2.641 g, 10.54 mmol, 96.3%): Rf 0.91(hexanes/Et2O, 4:1); 1H NMR (300 MHz, CDCl₃) δ 5.92 (dd, J=17.0, 10.2Hz, 1H, H-2), 5.44 (d, J=17.0 Hz, 1H, H-1), 5.28 (bs, 1H, H-7), 5.22 (p,J=1.5 Hz, 1H, H-7), 5.07 (d, J=10.2 Hz, 1H, H-1), 4.36 (s, 1H, H-10),1.89 (s, 3H, H-8), 1.56 (s, 3H, H-9), 0.95-1.14 (m, 14H, H-11, 12); 13CNMR (300 MHz, CDCl₃) δ 142.6 (C-2), 126.4 (C-6), 121.6 (C-7), 112.8(C-1), 89.9 (C-4), 86.9 (C-5), 70.5 (C-3), 31.6 (C-9), 23.3 (C-8), 17.6(C-12), 17.55 (C-12), 17.53 (C-12), 12.7 (C-11), 12.6 (C-11); HRMS calcdfor C₁₅H₂₆OSi (M+) 250.1753. found 250.1744.

(3-Cyclohexenylprop-2-ynyloxy)diisopropylsilane [7e]

3-Cyclohexenylprop-2-yn-1-ol (61) (1.236 g, 12.86 mmol), triethylamine(1.30 g, 12.85 mmol), dimethylaminopyridine (0.152 g, 1.267 mmol) anddiisopropylchlorosilane (1.918 g, 12.73 mmol) were used to yieldcompound 7e (1.680 g, 6.71 mmol, 52.7%) as a colorless, clear oilysubstance after purification by flash chromatography: R_(f) 0.85(hexanes/Et₂O, 4:1); ¹H NMR (500 MHz, CDCl₃) δ 6.08 (h, J=1.8 Hz, 1H,H-5), 4.48 (s, 2H, H-1), 4.20 (s, 2H, H-10), 1.98-2.17 (m, 4H, H6-9),1.49-1.71 (m, 4H, H6-9), 0.96-1.12 (m, 14H, H-11, 12). ¹³C NMR (300 MHz,CDCl₃) δ 134.8 (C-5), 120.3 (C-4), 87.1 (C-2/3), 84.4 (C-2/3), 54.3(C-1), 29.0 (C₆₋₉), 25.6 (C₆₋₉), 22.2 (C₆₋₉), 21.5 (C₆₋₉), 17.3 (C-12),17.2 (C-12), 12.3 (C-11); HRMS calcd for C₁₅H₂₆NaOSi (M+Na)⁺ 273.1651.found 273.1639.

General Procedure for Synthesis of SiloxacyclopenteneContaining-1,3-Dienes by Potassium tert-Butoxide Catalyzedtrans-Hydrosilylation of Siloxy Substituted Enynes [8a, 8e].⁷ Potassiumtert-butoxide (10 mol %) taken in THF (10 mL) was added slowly ca. ˜10min. to a flask containing a solution of siloxy substituted enynes (8a,8e) in THF (10 mL). Stirring was continued for 1 h at ambienttemperature, and the reaction mixture was diluted with Et₂O (50 mL)followed by quenching with saturated NH₄Cl (100 mL) solution. Theorganic layer was separated and aqueous layers were extracted with Et₂O(3×50 mL). Combined organic layers were washed with brine, dried overMgSO₄. Volatiles were removed and the crude reaction mixture wassubjected to purification by using flash chromatography and/or achromatotron.

2,5-Dihydro-2,2-diisopropyl-3-(prop-1-en-2-yl)-1,2-oxasilole [8a]

(4-Methylpent-4-en-2-ynyloxy)diisopropylsilane (1.662 g, 7.90 mmol) andKO^(t)Bu (0.092 g, 0.8199 mmol) were used according to the generalprocedure mentioned above. The light brown clear solution was subjectedto column chromatography and yielded 8a as colorless, clear liquid(1.192 g, 5.666 mmol, 71.7%): R_(f)0.37 (hexanes/Et₂O, 15:1); ¹H NMR(500 MHz, CDCl₃) δ 6.68 (t, J=1.9 Hz, 1H, H-4), 4.99 (s, 1H, H-9), 4.80(s, 1H, H-9), 4.63 (dd, J=1.9, 0.9 Hz, 2H, H-5), 1.94 (s, 3H, H-10),1.09-1.19 (m, 2H, H-6), 1.04 (d, J=7.3 Hz, 6H, H-7), 0.99 (d, J=7.3 Hz,6H, H-7); ¹³C NMR (300 MHz, CDCl₃) δ 142.4 (C-4), 142.1 (C-8), 139.8(C-3), 116.3 (C-9), 72.7 (C-5), 20.6 (C-10), 17.3 (C-7), 17.0 (C-7),13.3 (C-6); Anal. calcd for C₁₂H₂₂OSi: C, 68.51; H, 10.54. Found: C,68.24; H, 10.61.

3-Cyclohexenyl-2,5-dihydro-2,2-diisopropyl-1,2-oxasilole [8e]

Using (3-cyclohexenylprop-2-ynyloxy)diisopropylsilane (0.715 g, 2.854mmol) and KO^(t)Bu (0.037 g, 0.330 mmol) produced a crude product as acolorless, clear liquid which upon flash chromatography yielded thetitle compound as clear colorless liquid; R_(f) 0.45 (hexanes/Et₂O,15:2). The isolated compound was found to have an impurity of about ˜20%with a close Rf value, hence the compound was further purified by usinga chromatotron (2.0 mm silica gel) (0.537 g, 2.144 mmol, 75.1%). ¹H NMR(300 MHz, CDCl₃) δ 6.56 (s, 1H, H-4), 5.57 (s, 1H, H-9), 4.61 (s, 1H,H-5), 2.17-2.26 (m, 2H, H-13), 2.03-2.16 (m, 2H, H-10), 1.64-1.75 (m,2H, H-12), 1.52-1.64 (m, 2H, H-11), 1.06-1.20 (m, 2H, H-6), 1.04 (d,J=6.6 Hz, 6H, H-7), 0.98 (d, J=6.8 Hz, 6H, H-7); ¹³C NMR (300 MHz,CDCl₃) δ 140.3 (C-3), 138.0 (C-4), 135.7 (C-8), 128.9 (C-9), 77.8 (C-5),26.2 (C-13), 26.0 (C-10), 22.8 (C-12), 22.4 (C-11), 17.4 (C-7), 17.1(C-7), 13.4 (C-6); HRMS calcd for C₁₅H₂₇OSi (M+H)⁺ 251.1831. found251.1828.

One-pot, Tandem Synthesis of Siloxy Substituted Enynes and TheirPotassium tert-Butoxide Catalyzed trans-Hydrosilylation Reactions Using1,1,3,3-Tetramethyldisilazane The respective Alkenynols (1.0 eq) weretaken in a 50 mL, round bottom flask kept in a water bath under N₂inlet. After the slow addition of tetramethyldisilazane (0.6 eq) over ˜5min using a syringe, water bath was removed and stirring continuedovernight at room temperature. Then volatiles were removed by rotovapand the crude reaction mixture was dissolved in THF (10 mL), and theflask was cooled in a water-bath at ambient temperature. The flask waspurged with N₂ for 2 min, then Ko^(t)Bu (10 mol %) was added in THF (3×5mL) solution over a period of 10 min. After the addition, the water bathwas removed and stirring continued for 1 h. at room temperature. Thereaction mixture was diluted with Et₂O (20 mL), followed by quenchingwith saturated NH₄Cl (50 mL). The organic layer was separated andaqueous layers were extracted with Et2O (3×20 mL). The combined organicswere washed with satd. NaCl solution (50 mL), dried over MgSO₄ andvolatiles were removed by rotovap. The crude reaction mixture waspurified by means of column chromatography or a chromatotron.

2,5-Dihydro-2,2-dimethyl-3-(prop-1-en-2-yl)-1,2-oxasilole [10a]

Using 4-methylpent-4-en-2-yn-1-ol (1.792 g, 18.64 mmol),1,1,3,3-tetramethyldisilazane (1.504 g, 11.28 mmol) and KO^(t)Bu (0.217g, 1.934 mmol) according to the above general procedure resulted a clearbrown colored crude reaction mixture which upon purification by columnchromatography yielded 10a as a clear colorless oil (2.014 g, 13.05mmol, 70.0%): Rf 0.68 (pentane/Et₂O, 3:1); ¹H NMR (500 MHz, CDCl₃) δ6.60 (as, 1H, H-4), 4.99 (s, 1H, H-8′), 4.82 (s, 1H, H-8″), 4.66 (s, 2H,H-5), 1.93 (s, 3H, H-9), 0.33 (as, 6H, H-6); ¹³C NMR (300 MHz, CDCl₃) δ142.2 (C-3), 141.3 (C-7), 141.2 (C-4), 115.7 (C-8), 71.9 (C-5), 20.4(C-9), 0.45 (C-6); HRMS calcd for C₈H₁₄OSi (M⁺) 154.0814. found154.0813.

(3-Cyclohexenylprop-2-ynyloxy)dimethylsilane [9e]

3-Cyclohexenylprop-2-yn-1-ol (2.509 g, 26.10 mmol) and1,1,3,3-tetramethyldisilazane (1.527 g, 11.45 mmol) were used accordingto the method mentioned above to produce the title compound as a brownclear liquid (3.916 g, 20.15 mmol, 77.2%). The crude reaction mixturewas analyzed by ¹H NMR to confirm the product formation and used inKOtBu catalyzed transhydrosilylation reaction.

3-Cyclohexenyl-2,5-dihydro-2,2-dimethyl-1,2-oxasilole [10e]

(3-Cyclohexenylprop-2-ynyloxy)dimethylsilane (2.77 g, 14.25 mmol) andKO^(t)Bu (0.160 g, 1.425 mmol) were used according to the generalprocedure. The brown oily crude reaction mixture was purified by flashchromatography using hexanes/Et₂O (6:1) as eluant to produce 10e as aclear colorless oil (1.437 g, 7.394 mmol, 51.9%), which was used inDiels-Alder reactions without further purification. Analytical sampleswere prepared from this chromatographic compound (0.235 g, 1.209 mmol)by using a chromatotron (2.0 mm, silica gel) yielded the title compoundas a colorless clear liquid in pure form (0.167 g, 0.859 mmol, 71.1%):R_(f) 0.34 (hexanes/Et₂O, 8:1); ¹H NMR (300 MHz, CDCl₃) δ 6.49 (s, 1H,H-4), 5.61 (s, 1H, H-8), 4.64 (s, 1H, H-5), 2.04-2.26 (m, 4H, H-9, 12),1.51-1.77 (m, 4H, H-10, 11), 0.32 (s, 6H, H-6); ¹³C NMR (300 MHz, CDCl₃)δ 142.6 (C-3), 136.9 (C-4), 135.2 (C-7), 128.8 (C-8), 72.0 (C-5), 26.1(C-9, 12), 22.6 (C-10/11), 22.4 (C-10/11), 0.74 (C-6); HRMS calcd forC₁₁H₁₈OSi (M⁺) 194.1127. found 194.1121.

General Procedure for Diels-Alder Reactions of SiloxacyclopenteneContaining-1,3-Dienes. Diene and dienophile were taken together in athick-walled sealed tube containing THF (5.0 mL), purged with N₂ forabout. 2 min and the tube was sealed and heated at 90° C. for thestipulated time. After which the seal was broken, and the volatiles wereremoved then the crude product was chromatographed to obtaincycloadducts almost in pure form.

(5αS,8αS,8βS)-5,5a-dihydro-3,3-diisopropyl-4-methyl-7-phenyl-1H-[1,2]oxasilolo[4,3-e]isoindole-6,8(3H,7H,8αH,8βH)-dione[11a] and(5αS,8αS,8βR)-5,5a-Dihydro-3,3-diisopropyl-4-methyl-7-phenyl-1H-[1,2]oxasilolo[4,3-e]isoindole-6,8(3H,7H,8αH,8βH)-dione[11b].

Compound 8a(2,5-Dihydro-2,2-diisopropyl-3-(prop-1-en-2-yl)-1,2-oxasilole) (0.496 g,2.358 mmol) and N-phenylmaleimide (0.201 g, 1.157 mmol) were takentogether according to above procedure and heated for 36 h. After removalof volatiles, the crude reaction mixture was dissolved in CHCl₃ (2.0 mL)followed by purification with flash chromatography using hexanes/Et₂O,2:1 resulting in elution of unreacted (excess) diene prior to thecycloadducts. After elution of unreacted (excess) diene, polarity of themobile phase was increased (hexanes/Et₂O, 1:1) to yield both the stereoisomers one after the other as in pure form (0.382 g, 0.996 mmol,86.2%).

Minor Isomer [11a]:

After eluting the excess diene with hexanes/diethyl ether (2:1),increasing the polarity yields (hexanes/Et₂O, 1:1) stereo isomer-11a(exo) as a viscous clear liquid almost in pure form (0.180 g, 0.469mmol, 47.1%): R_(f) 0.61 (hexanes/Et₂O, 1:1); ¹H NMR (500 MHz, CDCl₃) δ7.47 (t, J=7.4 Hz, 2H, H-15), 7.38 (t, J=7.4 Hz, 1H, H-16), 7.29 (d,J=7.4 Hz, 2H, H-14), 4.64 (dd, J=10.0, 7.6 Hz, 1H, H-9), 3.90 (dd,J=10.0, 8.6 Hz, 1H, H-9), 3.12 (ddd, J=17.8, 9.5, 8.1 Hz, 1H, H-5a),2.73 (dd, J=15.9, 8.1 Hz, 1H, H-5), 2.63 (t, J=9.5 Hz, 1H, H-8a),2.50-2.60 (m, 1H, H-8b), 2.22 (dd, J=15.9, 10.0 Hz, 1H, H-5), 1.96 (dd,J=1.7, 1.0 Hz, 3H, H-12), 1.11-1.20 (m, 2H, H-10), 1.09 (d, J=7.1, 3H,H-11), 1.02 (d, J=7.4, 6H, H-11), 1.00 (d, J=7.4, 3H, H-11); ¹³C NMR(300 MHz, CDCl₃) δ 178.3 (C-6), 177.9 (C-8), 143.9 (C-4), 131.7 (C-13),131.0 (C-3), 129.1 (C-15), 128.5 (C-16), 126.3 (C-14), 72.7 (C-9), 43.8(C-8a), 42.9 (C-8b), 39.7 (C-5a), 30.8 (C-5), 25.7 (C-12), 17.9 (C-11),17.3 (C-11), 17.1 (C-11), 13.1 (C-10), 12.6 (C-10); HRMS calcd forC₂₂H₃₀NO₃Si (M+H)⁺384.1995. found 384.1979.

¹H NMR (300 MHz, C₆D₆) δ 6.82 (d, J=7.9 Hz, 2H, H-14), 6.54 (t, J=7.9Hz, 2H, H-15), 6.40 (t, J=7.9 Hz, 1H, H-16), 4.20 (dd, J=9.8, 8.2 Hz,1H, H-9), 3.29 (dd, J=9.8, 8.8 Hz, 1H, H-9), 1.59-1.79 (m, 3H, H-5, 5a,8a), 1.25 (t, J=9.5 Hz, 1H, H-8b), 1.08 (dd, J=17.7, 12.6 Hz, 1H, H-5),0.93 (at, J=1.3 Hz, 3H, H-12), 0.48 (d, J=6.9 Hz, 3H, H-11), 0.36-0.46(m, 2H, H-10), 0.43 (d, J=5.4 Hz, 3H, H-11), 0.30-0.37 (m, 6H, H-11).

Major Isomer [11b]:

Once 11a elution was completed, polarity of the mobile phase wasgradually increased to 100% Et₂O, resulting in the elution of otherstereo isomer-11b (endo) as major product in the form of a colorlessclear viscous liquid (0.202 g, 0.527 mmol, 52.9%): R_(f) 0.24(hexanes/Et₂O, 1:1); ¹H NMR (500 MHz, C₆D₆) δ 7.40 (d, J=7.7 Hz, 2H,H-14), 7.12 (t, J=7.7 Hz, 2H, H-15), 6.97 (t, J=7.7 Hz, 1H, H-16), 4.94(dd, J=10.0, 7.7 Hz, 1H, H-9), 4.31 (dd, J=10.0, 9.0 Hz, 1H, H-9), 2.64(d, J=15.4 Hz, 1H, H-5), 2.36-2.52 (m, 2H, H-5a, 8a), 2.11-2.26 (m, 1H,H-8b), 1.68 (d, J=2.6 Hz, 3H, H-12), 1.59-1.73 (m, 1H, H-5), 1.06 (d,J=6.7 Hz, 3H, H-11), 1.01 (d, J=5.9 Hz, 3H, H-11), 0.94 (d, J=5.9 Hz,3H, H-11), 0.90 (d, J=6.7 Hz, 3H, H-11), 0.88-1.12 (m, 2H, H-10); ¹³CNMR (300 MHz, C₆D₆) δ 177.9 (C-6), 176.0 (C-8), 144.8 (C-4), 133.0(C-13), 132.5 (C-3), 128.8 (C-15), 128.1 (C-16), 126.4 (C-14), 67.7(C-9), 42.7 (C-8b), 40.8 (C-5a/8a), 40.7 (C-5a/8a), 31.1 (C-5), 26.3(C-12), 18.2 (C-11), 17.7 (C-11), 17.4 (C-11), 13.4 (C-10), 13.3 (C-10);HRMS calcd for C₂₂H₃₀NO₃NaSi (M+Na)⁺ 406.1814. found 406.1770. Theunreacted diene (excess) was recovered after the volatiles wererotovapped (0.093 g, 0.442 mmol, 36.8%).

¹H NMR (500 MHz, CDCl₃) δ 7.43 (t, J=7.9 Hz, 2H, H-15), 7.35 (t, J=7.9Hz, 1H, H-16), 7.19 (d, J=7.9 Hz, 2H, H-15), 4.65 (dd, J=10.1, 8.2 Hz,1H, H-9), 4.37 (dd, J=10.1, 8.8 Hz, 1H, H-9), 3.25-3.40 (m, 2H, H-5a,8a), 2.76-2.92 (m, 2H, H-5, 8b), 2.37 (dd, J=14.8, 6.3 Hz, 1H, H-5),1.93 (ad, J=2.5 Hz, 3H, H-12), 1.04-1.11 (m, 2H, H-10), 1.02 (d, J=7.3Hz, 3H, H-11), 0.98 (d, J=7.8 Hz, 3H, H-11), 0.97 (d, J=7.3 Hz, 3H,H-11), 0.94 (d, J=7.8 Hz, 3H, H-11).

(5αS,8αS,8βR)-5,5a-Dihydro-3,3,4-trimethyl-7-phenyl-1H-[1,2]oxasilolo[4,3-e]isoindole-6,8(3H,7H,8αH,8βH)-dione[1,2]

Compound 10a (2,5-Dihydro-2,2-dimethyl-3-(prop-1-en-2-yl)-1,2-oxasilole)(0.449 g, 2.910 mmol) and N-phenylmaleimide (0.195 g, 1.126 mmol) wereused according to the general procedure. After heating for 24 h, andflash chromatography resulted in eluting the excess unreacted diene(pentane/Et₂O, 2:1) as first eluant followed by increasing polarity ofthe mobile phase (100% Et₂O) yields 12 (endo) as a clear colorlessviscous liquid (0.323 g, 0.986 mmol, 87.5%): R_(f) 0.53 (100% Et₂O); ¹HNMR (500 MHz, C₆D₆) δ 7.34 (ad, J=7.8 Hz, 2H, H-13), 7.10 (at, J=7.8 Hz,2H, H-14), 6.96 (at, J=7.6 Hz, 1H, H-15), 5.02 (dd, J=10.3, 6.3 Hz, 1H,H-9), 4.28 (dd, J=10.3, 8.6 Hz, 1H, H-9), 2.56 (dd, J=14.6, 1.8 Hz, 1H,H-5), 2.46 (ddd, J=8.8, 6.8, 1.8 Hz, 1H, H-5a), 2.39 (dd, J=8.8, 6.8 Hz,1H, H-8a), 2.15-2.25 (m, 1H, H-8b), 1.65 (add, J=14.6, 6.8, 1H, H-5),1.60 (as, 3H, H-11), 0.20 (s, 3H, H-10), 0.14 (s, 3H, H-10); ¹³C NMR(300 MHz, C₆D₆) δ 177.8 (C-6/8), 176.3 (C-6/8), 144.4 (C), 135.6 (C),132.9 (C), 129.0 (C-14), 128.2 (C-15), 126.5 (C-13), 66.7 (C-9), 42.5(C-8b), 41.5 (C-8a), 40.9 (C-5a), 31.6 (C-5), 24.5 (C-11), −0.52 (C-10);HRMS calcd for C₁₈H₂₂NO₃Si (M+H)⁺ 328.1369. found 328.1364. Theunreacted (excess) diene (0.192 g, 1.244 mmol, 69.8%) was recoveredafter removal of volatiles by rotovap and was found in pure form: R_(f)0.78 (pentane/Et₂O, 1:2).

¹H NMR (500 MHz, CDCl₃) δ 7.44 (t, J=7.7 Hz, 2H, H-14), 7.35 (t, J=7.4Hz, 1H, H-15), 7.16 (ad, J=8.3 Hz, 2H, H-13), 4.72 (dd, J=10.1, 6.6 Hz,1H, H-9), 4.35 (dd, J=10.1, 8.5 Hz, 1H, H-9), 3.24-3.36 (m, 2H, H-5a,8a), 2.73-2.87 (m, 2H, H-5, 8b), 2.28 (dd, J=14.8, 6.3 Hz, 1H, H-5),1.89 (bs, 3H, H-11), 0.29 (s, 3H, H-10), 0.18 (s, 3H, H-10); ₁₃C NMR(300 MHz, CDCl₃) δ 178.5 (C-6), 176.8 (C-8), 144.6 (C-4), 134.7 (C-3),131.9 (C-12), 129.1 (C-13), 128.5 (C-15), 126.3 (C-14), 66.5 (C-9), 41.9(C-8b), 41.5 (C-8a), 40.8 (C-5a), 31.5 (C-5), 24.7 (C-11), −0.65 (C-10),−0.71 (C-10).

Synthesis of (buta-1,3-dien-2-yl)-dimethyl(phenyl)silane (1f).Chloroprene (1a) (4.575 g, 51.69 mmol) and phenyldimethylchlorosilane(8.034 g, 47.06 mmol) were used according to Method-A to yield lightyellow colored crude product (14.38 g) as a mixture of diene, 1f andxylenes. The crude product was subjected for fractional distillation atreduced pressure (20 mm, 45° C.) resulted in diene, 1f (7.772 g) as abrown colored liquid, which was further purified by flash chromatography(100% pentanes) to yield the title compound as a light yellow coloredliquid in pure form (8.36 g, 44.39 mmol, 96.8%): R_(f) 0.63 (100%pentanes); ¹H NMR (500 MHz, CDCl₃) δ 7.49-7.55 (m, 2H, H-7), 7.31-7.37(m, 3H, H-8, 9), 6.46 (dd, J=17.7, 10.9 Hz, 1H, H-3), 5.88 (d, J=3.2 Hz,1H, H-1), 5.51 (d, J=3.2 Hz, 1H, H-1), 5.10 (d, J=17.7 Hz, 1H,H-4_(trans)), 5.00 (d, J=10.9 Hz, 1H, H-4_(cis)), 0.43 (s, 9H, H-5); ¹³CNMR (300 MHz, CDCl₃) δ 147.6 (C-2), 141.1 (C-3), 138.2 (C-6), 133.9(C-7), 130.4 (C-1), 129.0 (C-9), 127.8 (C-8), −2.3 (C-5); HRMS calcd forC₁₂H₁₆Si (M⁺) 188.1021. found 188.1020. Anal. calcd for C₁₂H₁₆Si: C,76.53; H, 8.56.

Synthesis of Trimethyl[(E)-4-phenyl-1,3-butadien-2-yl]silane (2b).⁶1-[(E)-3-Bromobuta-1,3-dienyl]benzene (1.985 g, 9.494 mmol) andtrimethylsilylchloride (1.37 g, 12.61 mmol) were used according toMethod-B, results the crude compound as dark brown liquid. The cruderesidue after purification by flash chromatography (hexanes/Et₂O, 9:1)yields compound 2b as brown-yellow oil (1.562 g, 7.728 mmol, 85%).Spectroscopic data was not reported earlier:^(7,8) R_(f) 0.15(hexanes/Et₂O, 9:1); ¹H NMR (500 MHz, CDCl₃) δ 7.43 (ad, J=7.7 Hz, 2H,H-6), 7.34 (t, J=7.7 Hz, 1H, H-7), 7.24 (t, J=7.4 Hz, 1H, H-8), 6.94 (d,J=16.5 Hz, 1H, H-3), 6.64 (d, J=16.5 Hz, 1H, H-4), 5.89 (d, J=3.0 Hz,1H, H-1), 5.53 (d, J=3.0 Hz, 1H, H-1), 0.27 (s, 9H, H-9); ¹³C NMR (300MHz, CDCl₃) δ 148.9 (C-2), 137.7 (C-5), 134.0 (C-3), 130.5 (C-4), 128.6(C-1), 128.5 (C-7), 127.3 (C-8), 126.3 (C-6), 0.8 (C-9); HRMS calcd forC₁₃H₁₈Si (M⁺) 202.1178. Anal. calcd for C₁₃H₁₈Si: C, 77.16; H, 8.97.

Synthesis of (1-cyclohexylideneprop-2-en-2-yl)trimethylsilane (3b).Chlrotrimethylsilane (0.685 g, 6.303 mmol) and(2-bromoallylidene)cyclohexene (3a) (0.929 g, 4.644 mmol) were usedaccording to Method-B. The resulted dark brown crude residue afterpurification by flash chromatography (hexanes/Et₂O, 15:1→9:1) yieldedcompound 3b as a brown-yellow oil (0.483 g, 2.488 mmol, 47.3%): R_(f)0.84 (hexanes/Et₂O, 15:1); ¹H NMR (500 MHz, CDCl₃) δ 5.71 (s, 1H, H-1),5.40-5.49 (m, 2H, H-3), 2.10-2.23 (m, 4H, H-5,9), 1.54-1.60 (m, 4H,H-6,8), 1.41-1.50 (m, 2H, H-7), 0.07 (s, 9H, H-10); ¹³C NMR (300 MHz,CDCl₃) δ 150.3 (C-2), 140.5 (C-4), 125.1 (C-3), 123.5 (C-1), 37.4(C-5/9), 29.3 (C-5/9), 29.0 (C-6/8), 28.3 (C-7), 26.9 (C-6/8), −1.95(C-10); HRMS calcd for C₁₂H₂₂Si (M⁺) 194.1491. found 194.1489.

General Procedure for Diels-Alder Reactions.

Synthesis of3a,4,7,7a-tetrahydro-5-[dimethyl(phenyl)silyl]-2-phenyl-2H-isoindole-1,3-dione(6a); ¹H NMR (500 MHz, CDCl₃) δ 7.41-7.54 (m, 4H), 7.29-7.41 (m, 4H),7.09-7.20 (m, 2H, H-10), 6.34 (p, J=3.2 Hz, 1H, H-6), 3.18-3.30 (m, 2H,H-3a,7a), 2.71-2.88 (m, 2H, H-4,7), 2.22-2.36 (m, 2H, H-4,7), 0.36 (s,3H, H-16), 0.35 (s, 3H, H-16); ¹³C NMR (300 MHz, CDCl₃) δ 179.1 (C-1/3),178.7 (C-1/3), 140.7 (C-5), 138.4 (C-6), 137.0 (C-12), 133.9 (CH), 132.0(C-8), 129.2 (CH), 129.0 (CH), 128.4 (CH), 127.8 (CH), 126.3 (CH), 39.3(C-3a/7a), 39.2 (C-3a/7a), 26.4 (C-4/7), 25.0 (C-4/7), −3.88 (C-16),−3.89 (C-16); HRMS calcd for C₂₂H₂₃NO₂Si (M⁺) 361.1498. found 361.1490.Anal. calcd for C₂₂H₂₃NO₂Si: C, 73.10; H, 6.42. Found: C, 72.63; H,6.38.

General Procedure for the Cross-Coupling Reactions. These reactions werecarried out by analogy to a reported literature procedure. Diels-Aldercycloadduct (1.0 eq), Pd(OAc)₂ (10 mol %), PPh₃ (20 mol %) andarylhalide (1.2 eq) were taken in a seal tube charged with microstir-bar, and dissolved in dis. DMF (5 mL). This transparent yellowcolored reaction mixture was stirred to homogenate followed by additionof TBAF (1.2 eq) dissolved in THF (0.5 mL), which results in a reactionmixture dark brown in color, which was purged with N₂, and heated in anoil bath for 2 h at 90° C. During the course of reaction, the reactionmixture turned dark black and the formation of active palladium species(Pd^(II)→Pd⁰) was also noticed as the catalyst slowly turned to blacksolid. The reaction mixture was then quenched with water (50 mL), andextracted with Et₂O (4×30 mL). The combined organic layers were againwashed with water (2×75 mL), dried over MgSO₄ and volatiles were removedby rotary evaporation. The resulting cross-coupled cycloadduct residuewas purified by flash chromatography.

Synthesis of(3aR,7aS)-5-(2-methoxyphenyl)-2-phenyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione(7a). Cycloadduct 4a (0.101 g, 0.252 mmol), Pd(OAc)₂ (0.020 g, 0.034mmol), PPh₃ (0.024 g, 0.092 mmol), 2-iodoanisole (0.084 g, 0.359 mmol)and TBAF (0.110 g, 0.349 mmol) were used according to the generalprocedure mentioned above. The resulting brown colored oily crudereaction mixture was subjected to flash chromatography to yield thecross-coupled product 7a as a yellow solid (0.048 g, 0.144 mmol, 57.1%):R_(f) 0.42 (diethyl ether/hexanes, 2:1); ¹H NMR (500 MHz, CDCl₃) δ 7.44(t, J=8.1 Hz, 2H, H-10), 7.37 (t, J=7.5 Hz, 1H, H-11), 7.18-7.25 (m, 3H,H-9, 15), 7.08 (d, J=7.5 Hz, 1H, H-17), 6.90 (t, J=7.5 Hz, 1H, H-16),6.83 (d, J=8.1 Hz, 1H, H-14), 6.03 (p, J=3.4 Hz, 1H, H-6), 3.67 (s, 3H,H-18), 3.36 (ddd, J=9.1, 7.7, 2.4 Hz, 1H, H-3a), 3.32 (ddd, J=9.1, 6.7,2.6 Hz, 1H, H-7a), 3.07 (dd, J=15.4, 2.4 Hz, 1H, H-4), 2.94 (ddd,J=15.4, 6.7, 2.6 Hz, 1H, H-7), 2.63 (ddt, J=15.4, 7.7, 2.4 Hz, 1H, H-4),2.37-2.50 (m, 1H, H-7); ¹³C NMR (300 MHz, CDCl₃) δ 179.2 (C-1), 178.8(C-3), 156.5 (C-13), 139.5 (C-5), 132.3 (C-8), 130.9 (C-12), 129.2(C-11/17), 129.0 (C-10), 128.8 (C-11/17), 128.5 (C-15), 126.7 (C-9),125.1 (C-6), 120.6 (C-16), 110.5 (C-14), 54.9 (C-18), 40.0 (C-3a/7a),39.8 (C-3a/7a), 28.9 (C-4), 24.5 (C-7); HRMS calcd for C₂₁H₁₉NO₃ (M⁺)333.1365, Anal. calcd for C₂₁H₁₉NO₃: C, 75.66; H, 5.74.

Synthesis of(3aR,7aS)-5-(3-methoxyphenyl)-2-phenyl-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione(7b). Cycloadduct 4a (0.100 g, 0.250 mmol), Pd(OAc)₂ (0.028 g, 0.047mmol), PPh₃ (0.024 g, 0.088 mmol), 3-iodoanisole (0.126 g, 0.538 mmol)and TBAF (0.128 g, 0.406 mmol) were used according to the generalprocedure mentioned above. The resulting brown colored oily crudereaction mixture was subjected to flash chromatography to yield thecross-coupled product 7b as a brown colored oily substance (0.073 g,0.219 mmol, 87.7%): R_(f) 0.15 (diethyl ether/hexanes, 2:1); ¹H NMR (500MHz, CDCl₃) 7.44 (t, J=8.1 Hz, 2H, H-10), 7.37 (t, J=7.5 Hz, 1H, H-11),7.18-7.25 (m, 3H, H-9, 15), 7.08 (d, J=7.5 Hz, 1H, H-17), 6.90 (t, J=2.1Hz, 1H), 6.81 (dd, J=6.8, 2.5 Hz, 1H), 6.27 (p, J=3.4 Hz, 1H, 1-6), 3.80(s, 3H, H-18), 3.43 (ddd, J=9.4, 7.0, 2.5 Hz, 1H), 3.34 (ddd, J=9.4,7.2, 2.5 Hz, 1H), 3.24 (dd, J=15.3, 2.5 Hz, 1H), 2.93 (ddd, J=15.3, 7.0,2.5 Hz, 1H), 2.64 (ddt, J=15.3, 6.8, 2.3 Hz, 1H), 2.37-2.51 (m, 1H), ¹³CNMR (300 MHz, CDCl₃) δ 179.0 (C-), 178.8 (C-), 159.8 (C-), 141.9 (C-),140.0 (C-), 132.0 (C-), 129.6 (C-), 129.1 (C-), 128.6 (C-), 126.4 (C-),123.4 (C-), 118.0 (C-), 113.1 (C-), 111.2 (C-), 55.2 (C-), 40.1 (C-),39.5 (C-), 27.7 (C-), 25.3 (C-); HRMS calcd for C₂₁H₁₉NO₃ (M⁺) 333.1365,Anal. calcd for C₂₁H₁₉NO₃: C, 75.66; H, 5.74.

Synthesis of(3aR,7aS)-2-phenyl-5-(4-(trifluoromethyl)phenyl)-3a,4,7,7a-tetrahydro-1H-isoindole-1,3(2H)-dione(7d). Cycloadduct 4a (0.099 g, 0.247 mmol), Pd(OAc)₂ (0.023 g, 0.039mmol), PPh₃ (0.024 g, 0.092 mmol), 1-iodo-4-(trifluoromethyl)benzene(0.132 g, 0.485 mmol) and TBAF (0.098 g, 0.311 mmol) were used accordingto the general procedure mentioned above. The resulting brown coloredoily crude reaction mixture was subjected to flash chromatography toyield the cross-coupled product 7d as a colorless clear liquid (0.082 g,0.221 mmol, 89.3%): R_(f) 0.35 (diethyl ether/hexanes, 2:1); ¹H NMR (500MHz, CDCl₃) δ 7.58 (d, J=8.4 Hz, 2H, H-13), 7.46 (d, J=8.4 Hz, 2H,H-14), 7.42 (t, J=7.5 Hz, 2H, H-10), 7.36 (t, J=7.5 Hz, 1H, H-11), 7.14(t, J=7.5 Hz, 2H, H-9), 6.31 (p, J=3.4 Hz, 1H, H-6), 3.47 (ddd, J=9.4,7.1, 2.7 Hz, 1H, H-3a), 3.38 (ddd, J=9.4, 7.6, 2.5 Hz, 1H, H-7a), 3.27(dd, J=15.3, 2.5 Hz, 1H, H-4), 2.99 (ddd, J=15.6, 7.1, 2.3 Hz, 1H, H-7),2.65 (ddt, J=15.3, 6.7, 2.5 Hz, 1H, H-4), 2.37-2.54 (m, 1H, H-7); ¹³CNMR (300 MHz, CDCl₃) δ 178.8 (C-3), 178.7 (C-1), 143.7 (C-12), 139.1(C-5), 131.8 (C-15), 129.1 (C-10), 128.7 (C-11), 126.3 (C-9), 125.8(C-13, 14), 125.6 (q, C-16), 125.4 (C-6), 40.0 (C-3a), 39.3 (C-7a), 27.4(C-4), 25.4 (C-7); HRMS calcd for C₂₁H₁₆F₃NO₂ (M⁺) 371.1133, Anal. calcdfor C₂₁H₁₆F₃NO₂: C, 67.92; H, 4.34.

In an embodiment, the present invention is directed to a compoundselected from the group consisting of Formula I, Formula II, FormulaIII, Formula IV, Formula VI, and Formula VII:

wherein A is a member selected from the group consisting of silicon,platinum, rhodium, boron, arsenic and palladium;

X and X′ are independently aliphatic or aromatic groups which are eachindependently selected from the group consisting of alkyl, alkenyl,alkynyl, aryl, heteroaryl, heterocyclyl, wherein the alkyl, alkenyl, andalkynyl, groups may be substituted by one or more heteroatoms, and whenone or more heteroatoms is present in the alkyl, alkenyl, and alkynylgroups and in the heteroaryl and heterocyclyl groups, the heteroatomsare selected from the group consisting of nitrogen, phosphorous,arsenic, antimony, bismuth, germanium, tin, oxygen, sulfur, selenium,tellurium, boron, aluminum, gallium, indium, germanium, and silicon,

and wherein all of the alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl groups also may be optionally substituted by one or more ofthe following: alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl,halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy, amino, imino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,nitroso, and thioxo;

R₁, R₂, R₃, and R₄ are each independently selected from the groupconsisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl, halo, cyano, hydroxy, mercapto, sulfonyl, sulfoxy, amino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,and nitroso, or

R₁ and R₂ together with the atoms connected to them or R₃ and R₄together with the atoms connected to them may form a spiro C₄₋₈cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; or

R₁ and R₃ together with the atoms connected to them or R₂ and R₄together with the atoms connected to them may form a C₃₋₁₀ cycloalkylgroup that may optionally contain one or more heteroatoms selected fromthe group consisting of nitrogen, phosphorous, arsenic, antimony,bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium, boron,aluminum, gallium, indium, germanium, and silicon; and wherein

Y is a counterion.

In a variation of the embodiment, A is silicon. In an alternatevariation, X and X′ represent an alkyl or alkenyl group optionallysubstituted by nitrogen, X and X′ represent alkyl substituted bynitrogen, or X and X′ represent an aryl group. In a variation, the arylgroup is phenyl. In a variation, X is heteroaryl or heterocyclyl, or Xis an alkyl, alkenyl, or alkynyl group substituted by one or moreheteroatoms, the heteroatoms in the heteroaryl or heterocyclyl group orthe heteroatoms in the alkyl, alkenyl, and alkynyl groups are one ormore members selected from the group consisting of nitrogen, oxygen,sulfur, and selenium.

In another embodiment, Y is sodium, potassium, or tetra-butyl ammonium.In a variation of an embodiment, A is platinum.

In an embodiment, R₁, R₂, R₃, and R₄ together with the carbons to whichthey are attached is 1-phenyl-1H-pyrrole-2,5-dione.

In an embodiment, the present invention relates to a compound that isselected from the group consisting of

wherein Y is a potassium ion.

In an embodiment, the present invention relates to a method of makingcompounds selected from the group consisting of Formulas I, II, and VII

comprising reacting the dienes selected from the group consisting ofFormulas III, IV and VI,

respectively with the dienophile of Formula V

wherein in Formulas I, II, III, IV, V, VI, VII, A is a member selectedfrom the group consisting of silicon, platinum, rhodium, boron, arsenicand palladium;

X and X′ are independently aliphatic or aromatic groups which are eachindependently selected from the group consisting of alkyl, alkenyl,alkynyl, aryl, heteroaryl, heterocyclyl, wherein the alkyl, alkenyl, andalkynyl, groups may be substituted by one or more heteroatoms, and whenone or more heteroatoms is present in the alkyl, alkenyl, and alkynylgroups and in the heteroaryl and heterocyclyl groups, the heteroatomsare selected from the group consisting of nitrogen, phosphorous,arsenic, antimony, bismuth, germanium, tin, oxygen, sulfur, selenium,tellurium, boron, aluminum, gallium, indium, germanium, and silicon,

and wherein all of the alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl groups also may be optionally substituted by one or more ofthe following: alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl,halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy, amino, imino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,nitroso, and thioxo;

R₁, R₂, R₃, and R₄ are each independently selected from the groupconsisting of hydrogen, alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl, halo, cyano, hydroxy, mercapto, sulfonyl, sulfoxy, amino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,and nitroso, or

R₁ and R₂ together with the atoms connected to them or R₃ and R₄together with the atoms connected to them may form a spiro C₄₋₈cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; or

R₁ and R₃ together with the atoms connected to them or R₂ and R₄together with the atoms connected to them may form a C₃₋₁₀ cycloalkylgroup that may optionally contain one or more heteroatoms selected fromthe group consisting of nitrogen, phosphorous, arsenic, antimony,bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium, boron,aluminum, gallium, indium, germanium, and silicon;

and wherein Y is a counterion.

In a variation of the embodiment, A is silicon. In a variation, X and X′independently represent an alkyl or alkenyl group substituted by one ormore nitrogen atoms or X and X′ represent an aryl group. In anothervariation, X and X′ represent a phenyl group or an alkyl groupsubstituted by a nitrogen atom.

In an embodiment, the diene is selected from the group consisting of

In a variation, Y is potassium, sodium, or tetrabutyl ammonium. Inanother variation, one of R₁ and R₂ is an electron withdrawing group. Inanother variation, R₁, R₂, R₃, and R₄ together with the carbons to whichthey are attached is 1-phenyl-1H-pyrrole-2,5-dione.

In an embodiment, the present invention relates to a compound of FormulaIX

wherein B is C or Si; R₂₁ and R₂₂ are independently hydrogen, alkyl,alkenyl, or R₂₁ and R₂₂ in conjunction with the carbon to which they areattached form a 3 to 8 membered carbocyclo ring; R₂₃ is hydrogen, alkyl,alkenyl, hydroxy, aryl or —O—Si(R₂₆)(R₂₇)(R₂₈); R₂₄, R₂₅, R₂₆, R₂₇, andR₂₈ are each independently hydrogen, alkyl, alkenyl, or aryl.

In a variation, the compound contains silicon or alternatively, one of Band R₂₃ contains silicon.

In a variation, all of R₂₁, R₂₂, R₂₃, R₂₄, R₂₅, R₂₆, R₂₇, and R₂₈ arenot hydrogen. In another variation, the aryl group is phenyl. In anothervariation, R₂₁ and R₂₂ together with the carbon to which they attachedform a cyclohexenyl group.

The following references are noted:

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Although specific embodiments are shown to generate cyclic compounds ina Diels Alder type fashion, the present invention should not beconstrued so as to be limited to just those embodiments. It should beunderstood that the above examples are given only for the sake ofshowing that the reaction process can make a particular compound in thedisclosed genus. The above procedure can be generalized so that all ofthe compounds in the disclosed genus can be made. Any one or morefeature from any of the disclosed embodiments above can be combined withany one or more feature from any other embodiment. The above writtendescription is not meant to limit the invention in any way. Rather, thebelow claims define the invention.

1. A compound selected from the group consisting of Formula III, FormulaIV, Formula I, Formula II, Formula VI, and Formula VII:

wherein A is a member selected from the group consisting of silicon andboron; X and X′ are independently aliphatic or aromatic groups which areeach independently selected from the group consisting of alkyl, alkenyl,alkynyl, aryl, heteroaryl, heterocyclyl, wherein the alkyl, alkenyl, andalkynyl, groups may be substituted by one or more heteroatoms, and whenone or more heteroatoms is present in the alkyl, alkenyl, and alkynylgroups and in the heteroaryl and heterocyclyl groups, the heteroatomsare selected from the group consisting of nitrogen, phosphorous,arsenic, antimony, bismuth, germanium, tin, oxygen, sulfur, selenium,tellurium, boron, aluminum, gallium, indium, germanium, and silicon, andwherein all of the alkyl, alkenyl, alkynyl, aryl, heteroaryl,heterocyclyl groups also may be optionally substituted by one or more ofthe following: alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl,halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy, amino, imino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,nitroso, and thioxo; R₁, R₂, R₃, and R₄ are each independently selectedfrom the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl,heteroaryl, heterocyclyl, halo, cyano, hydroxy, mercapto, sulfonyl,sulfoxy, amino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, and nitroso, or R₁ and R₂ together with the atomsconnected to them or R₃ and R₄ together with the atoms connected to themmay form a spiro C₄₋₈ cycloalkyl group that may optionally contain oneor more heteroatoms selected from the group consisting of nitrogen,phosphorous, arsenic, antimony, bismuth, germanium, tin, oxygen, sulfur,selenium, tellurium, boron, aluminum, gallium, indium, germanium, andsilicon; or R₁ and R₃ together with the atoms connected to them or R₂and R₄ together with the atoms connected to them may form a C₃₋₁₀cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; and wherein Yis a counterion.
 2. The compound of claim 1, wherein A is silicon. 3.The compound of claim 2, wherein X and X′ represent an alkyl or alkenylgroup optionally substituted by nitrogen.
 4. The compound of claim 3,wherein X and X′ represent alkyl substituted by nitrogen.
 5. Thecompound of claim 2, wherein X and X′ represent an aryl group.
 6. Thecompound of claim 5, wherein the aryl group is phenyl.
 7. The compoundof claim 2, wherein Y is sodium, potassium, or tetra-butyl ammonium. 8.The compound of claim 2, wherein when X is heteroaryl or heterocyclyl,or X is an alkyl, alkenyl, or alkynyl group substituted by one or moreheteroatoms, the heteroatoms in the heteroaryl or heterocyclyl group orthe heteroatoms in the alkyl, alkenyl, and alkynyl groups are one ormore members selected from the group consisting of nitrogen, oxygen,sulfur, and selenium.
 9. The compound of claim 2, wherein R₁, R₂, R₃,and R₄ together with the carbons to which they are attached is1-phenyl-1H-pyrrole-2,5-dione.
 10. The compound of claim 2, wherein thecompound is selected from the group consisting of

wherein Y is a potassium ion.
 11. A method of making compounds selectedfrom the group consisting of Formulas I, II, and VII

comprising reacting the dienes selected from the group consisting ofFormulas III, IV and VI,

respectively with the dienophile of Formula V

wherein in Formulas I, II, III, IV, V, VI, VII, A is a member selectedfrom the group consisting of silicon and boron; X and X′ areindependently aliphatic or aromatic groups which are each independentlyselected from the group consisting of alkyl, alkenyl, alkynyl, aryl,heteroaryl, heterocyclyl, wherein the alkyl, alkenyl, and alkynyl,groups may be substituted by one or more heteroatoms, and when one ormore heteroatoms is present in the alkyl, alkenyl, and alkynyl groupsand in the heteroaryl and heterocyclyl groups, the heteroatoms areselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon, and whereinall of the alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclylgroups also may be optionally substituted by one or more of thefollowing: alkyl, alkenyl, alkynyl, aryl, heteroaryl, heterocyclyl,halo, cyano, oxo, hydroxy, mercapto, sulfonyl, sulfoxy, amino, imino,alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino, di-alkylamino, nitro,nitroso, and thioxo; R₁, R₂, R₃, and R₄ are each independently selectedfrom the group consisting of hydrogen, alkyl, alkenyl, alkynyl, aryl,heteroaryl, heterocyclyl, halo, cyano, hydroxy, mercapto, sulfonyl,sulfoxy, amino, alkylthio, alkoxy, alkoxyalkyl, mono-alkylamino,di-alkylamino, nitro, and nitroso, or R₁ and R₂ together with the atomsconnected to them or R₃ and R₄ together with the atoms connected to themmay form a spiro C₄₋₈ cycloalkyl group that may optionally contain oneor more heteroatoms selected from the group consisting of nitrogen,phosphorous, arsenic, antimony, bismuth, germanium, tin, oxygen, sulfur,selenium, tellurium, boron, aluminum, gallium, indium, germanium, andsilicon; or R₁ and R₃ together with the atoms connected to them or R₇and R₄ together with the atoms connected to them may form a C₃₋₁₀cycloalkyl group that may optionally contain one or more heteroatomsselected from the group consisting of nitrogen, phosphorous, arsenic,antimony, bismuth, germanium, tin, oxygen, sulfur, selenium, tellurium,boron, aluminum, gallium, indium, germanium, and silicon; and wherein Yis a counterion.
 12. The method of claim 11, wherein A is silicon. 13.The method of claim 12, wherein X and X′ independently represent analkyl or alkenyl group substituted by one or more nitrogen atoms or Xand X′ represent an aryl group.
 14. The method of claim 12, wherein Xand X′ represent a phenyl group or an alkyl group substituted by anitrogen atom.
 15. The method of claim 14, wherein the diene is selectedfrom the group consisting of

wherein Y is a potassium ion.
 16. The method of claim 12, wherein Y ispotassium, sodium, or tetrabutyl ammonium.
 17. The method of claim 12,wherein one of R₁ and R₂ is an electron withdrawing group.
 18. Themethod of claim 11, wherein R₁, R₂, R₃, and R₄ in Formula V togetherwith the carbons to which they are attached is1-phenyl-1H-pyrrole-2,5-dione.